Golf ball incorporating functionalized inorganic aluminosilicate ceramic microspheres in at least one core layer

ABSTRACT

Golf balls of the invention include at least one core layer comprised or consisting of a homogenous rubber-based core composition with a plurality of functionalized inorganic aluminosilicate ceramic microspheres dispersed throughout without agglomerating to create a relatively higher cross-link density of the core layer material. In golf balls of the invention, cross-link density gradients may be created between core layers by pre-electing the presence/absence, amount, type, and degree of functionalization of the plurality of functionalized inorganic aluminosilicate ceramic microspheres in two given core layers to target important properties such as resilience/CoR and desired playing characteristics such as distance.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 17/355,434, filed Jun. 23, 2021, which claims the benefit ofU.S. Provisional Application No. 63/048,870, filed Jul. 7, 2020, theentire disclosures of which are hereby incorporated herein by reference.

FIELD OF THE INVENTION

Golf balls including at least one core layer comprised or consisting ofa rubber-based composition having a relatively higher cross-link densityand CoR.

BACKGROUND OF THE INVENTION

Both professional and amateur golfers use multi-piece, solid golf ballstoday. Basically, a two-piece solid golf ball includes a solid coreprotected by a cover. The core is typically made of a natural orsynthetic rubber such as polybutadiene, styrene butadiene, orpolyisoprene. The cover may be made of a variety of materials includingethylene acid copolymer ionomers, polyamides, polyesters, polyurethanes,and/or polyureas.

Three-piece, four-piece, and even five-piece balls have become morepopular over the years. Golfers are playing with multi-piece balls forseveral reasons, including availability of lower-cost materials and thedevelopment of new manufacturing technologies which make it possible andcost-effective to produce a multi-layered golf ball having uniquedesirable resulting performance characteristics. In multi-layered golfballs, each of the core, intermediate layer and cover can be single ormulti-layered, and properties such as hardness, modulus, compression,resilience, core diameter, intermediate layer thickness and coverthickness can be preselected and coordinated to target playcharacteristics of the resulting golf ball such as spin, initialvelocity and feel.

In this regard, the core acts as an engine or spring for the golf ball.Thus, the composition and construction of the core is a key factor indetermining the resiliency and rebounding performance of the ball. Ingeneral, rebounding performance is determined by calculating initialvelocity of the golf ball after being struck by a golf club face and itsoutgoing velocity after making impact with a hard surface. Golf ballswith a higher rebound velocity have a higher CoR value, retain moretotal energy when struck with a club, and have longer flight distance asopposed to golf balls with lower CoR values. These properties areparticularly important for long distance shots.

The resiliency or CoR of the core can be increased by increasing thecross-link density of the core material. Unfortunately, conventionaladditives/fillers used in rubber-based formulations for this purposeheretofore tend to undesirably agglomerate within the rubbercomposition, and this has remained a recurring issue.

A special need therefore remains to develop golf balls incorporatingcross-link density-increasing ingredients that will disperse throughoutthe rubber-based composition without agglomerating and meanwhile canimprove important core properties such as resilience/CoR withoutsacrificing golf ball durability, “feel” and other important golf ballproperties. Such golf balls, if producible cost effectively withinalready existing golf ball manufacturing systems would be particularlydesirable. The golf balls of the invention and methods of making sameaddress and fulfill these needs.

SUMMARY OF THE INVENTION

Accordingly, golf balls of the invention include rubber-basedcompositions comprising a plurality of functionalized inorganicaluminosilicate ceramic microspheres which disperse throughout thepolymer matrix without agglomerating due at least in part to thephysical structure and chemistry associated with the functionalizedinorganic aluminosilicate ceramic microspheres. Meanwhile, thefunctionalized inorganic aluminosilicate ceramic microspheres canfavorably increase the cross-link density of the rubber composition andin some embodiments even reduce the normalized moisture vaper transitionrate of the rubber composition without negatively impacting golf balldurability, feel and other important physical and chemical propertiesand playing characteristics.

Thus, in one embodiment, a golf ball of the invention comprises a coreand a cover; wherein the core comprises the rubber composition having aplurality of functionalized inorganic aluminosilicate ceramicmicrospheres dispersed throughout.

In a specific embodiment, the functionalized inorganic aluminosilicateceramic microspheres are at least one of thiol-functionalized,vinyl-functionalized, methacrylate-functionalized,acrylate-functionalized, epoxy-functionalized, and/orcarboxyl-functionalized.

Preferably, the plurality may be included in the rubber composition inan amount of from about 1 phr to about 10 phr based on 100 phr ofpolybutadiene contained in the rubber composition.

The rubber composition may further comprise: a co-agent; zinc oxide;pentachlorothiophenol and/or salts thereof; peroxide; and optionally atleast one filler.

The co-agent may be selected from zinc salts of acrylic acid and/ormethacrylic acid, and is included in the rubber composition in an amountof from about 25 phr to about 45 phr based on 100 phr of polybutadienecontained in the rubber composition.

In a particular such embodiment, the co-agent is at least one of zincdiacrylate and zinc dimethacrylate.

In a specific embodiment, the salt of pentachlorothiophenol is zincpentachlorothiophenol and is included in the rubber composition in anamount of about 0.3 phr to about 0.7 phr based on 100 phr ofpolybutadiene contained in the rubber composition.

In a particular embodiment, the peroxide is included in the rubbercomposition in an amount of from about 0.5 phr to about 2.0 phr based on100 phr of polybutadiene contained in the rubber composition.

The filler may be included in an amount that is selected based on totalweight of all other ingredients such that the golf ball has a maximumweight of no greater than 45.93 g and/or 1.62 ounces as required by theUnited States Golf Association.

In a different embodiment, a golf ball of the invention comprises a coreand a cover; wherein the core comprises an inner core and an outer corelayer; the inner core comprising a first rubber composition, and theouter core layer comprising a second rubber composition; wherein onlyone of the first rubber composition and the second rubber compositionincludes a plurality of functionalized inorganic aluminosilicate ceramicmicrospheres dispersed throughout.

In a specific such embodiment, the second rubber composition of outercore layer includes the plurality of functionalized inorganicaluminosilicate ceramic microspheres and has a crosslink density that isgreater than a crosslink density of the first rubber composition of theinner core to create a positive crosslink density gradient from innercore to outer core layer.

In another specific embodiment, the second rubber composition of theouter core layer has a greater moisture vapor transmission rate than amoisture vapor transmission rate of the first rubber composition of theinner core to create a positive moisture vapor transmission rategradient from inner core to outer core layer.

In yet another embodiment, a golf ball of the invention comprises a coreand a cover, wherein the core comprises an inner core and an outer corelayer; wherein the inner core comprises a first rubber compositionincluding a first plurality of functionalized inorganic aluminosilicateceramic microspheres dispersed throughout; wherein the outer core layercomprises a second rubber composition including a second plurality offunctionalized inorganic aluminosilicate ceramic microspheres dispersedthroughout; wherein the first rubber composition and the second rubbercomposition differ at least in that the first plurality and the secondplurality differ as to at least one of: (i) amount of functionalizedinorganic aluminosilicate ceramic microspheres included in each of thefirst rubber composition and the second rubber composition, in parts perhundred, based on 100 phr of polybutadiene contained in the rubbercomposition; and/or (ii) type(s) of functionalized inorganicaluminosilicate ceramic microspheres included in each of the firstrubber composition and the second rubber composition; and/or (iii)degree of functionalization of the functionalized inorganicaluminosilicate ceramic microsphere included in each of the first rubbercomposition and the second rubber composition.

In one embodiment, the first plurality of functionalized inorganicaluminosilicate ceramic microspheres are at least one ofthiol-functionalized, vinyl-functionalized, methacrylate-functionalized,acrylate-functionalized epoxy-functionalized, and/orcarboxyl-functionalized; and the second functionalized inorganicaluminosilicate ceramic microspheres are at least one of differentlythiol-functionalized, vinyl-functionalized, methacrylate-functionalized,acrylate-functionalized, epoxy-functionalized, and/orcarboxyl-functionalized.

In another embodiment, the first functionalized inorganicaluminosilicate ceramic microspheres are included in the first rubbercomposition in an amount less than 5 phr based on 100 phr ofpolybutadiene contained in the rubber composition; and the secondfunctionalized inorganic aluminosilicate ceramic microspheres areincluded in the second rubber composition in an amount of from 5 phr toabout 10 phr based on 100 phr of polybutadiene contained in the rubbercomposition.

DETAILED DESCRIPTION

Accordingly, golf balls of the invention include at least one core layercomprised or consisting of a rubber-based composition having arelatively higher cross-link density and CoR. The at least one corelayer comprises or consists of a rubber-based composition incorporatinga plurality of functionalized inorganic aluminosilicate ceramicmicrospheres which disperse throughout the rubber composition withoutagglomerating due at least in part to the physical structure andchemistry associated with the functionalized inorganic aluminosilicateceramic microspheres, and meanwhile, can favorably increase cross-linkdensity (and lower the normalized moisture vaper transition rate in somecases) of the resulting rubber composition without negatively impactingother important physical and chemical properties of the core and playingcharacteristics of the golf ball in general. Thus, in one embodiment, agolf ball of the invention comprises a core and a cover; wherein thecore comprises a rubber composition including a plurality offunctionalized inorganic aluminosilicate ceramic microspheres dispersedthroughout.

In one embodiment, the core is a single core comprising a plurality offunctionalized inorganic aluminosilicate ceramic microspheres dispersedthroughout. In another embodiment, the core is a dual core wherein atleast one layer of the dual core includes a rubber compositioncomprising the plurality of functionalized inorganic aluminosilicateceramic microspheres dispersed throughout.

In a specific embodiment, the functionalized inorganic aluminosilicateceramic microspheres are at least one of thiol-functionalized,vinyl-functionalized, methacrylate-functionalized,acrylate-functionalized, epoxy-functionalized, and/orcarboxyl-functionalized.

Preferably, the plurality may be included in the rubber composition inan amount of from about 1 phr to about 10 phr based on 100 phr ofpolybutadiene contained in the rubber composition. In particularembodiments, the plurality may be included in the rubber composition inan amount of up to about 5 phr, or up to 5 phr, or from about 1 phr toabout 4 phr, or from 1 phr to 4 phr, or up to about 4 phr, or up to 4phr, or between about 1 phr and about 3 phr, or between 1 phr and 3 phr,or from about 2 phr to about 4 phr, or from 2 phr to 4 phr, or betweenabout 1 phr and about 5 phr, or between 1 phr and 5 phr, or from about 5phr to about 10 phr, or from 5 phr to 10 phr, or between about 5 phr andabout 10 phr, or between 5 phr and 10 phr, or from about 5 phr to about8 phr, or from 5 phr to 8 phr, or from about 6 phr to about 9 phr, orfrom 6 phr to 9 phr, or less than about 10 phr, or less than 10 phr, orless than about 8 phr, or less than 8 phr, or less than about 6 phr, orless than 6 phr, or less than about 4 phr, or less than 4 phr, or fromabout 2 phr to about 8 phr, or from 2 phr to 8 phr, or from about 2 phrto about 7 phr, or from 2 phr to 7 phr, or from about 2 phr to about 5phr, or from 2 phr to 5 phr, or from about 7 phr to about 10 phr, orfrom 7 phr to 10 phr based on 100 phr of polybutadiene contained in therubber composition.

The rubber composition may further comprise: a co-agent; zinc oxide;pentachlorothiophenol and/or salts thereof; peroxide; and optionally atleast one filler.

The co-agent may be selected from zinc salts of acrylic acid and/ormethacrylic acid, and is included in the rubber composition in an amountof from about 25 phr to about 45 phr based on 100 phr of polybutadienecontained in the rubber composition.

In a particular such embodiment, the co-agent is at least one of zincdiacrylate and zinc dimethacrylate.

In a specific embodiment, the salt of pentachlorothiophenol is zincpentachlorothiophenol and is included in the rubber composition in anamount of about 0.3 phr to about 0.7 phr based on 100 phr ofpolybutadiene contained in the rubber composition.

In a particular embodiment, the peroxide is included in the rubbercomposition in an amount of from about 0.5 phr to about 2.0 phr based on100 phr of polybutadiene contained in the rubber composition.

Filler may be included in an amount that is selected based on totalweight of all other ingredients such that the golf ball has a maximumweight of no greater than 45.93 g and/or 1.62 ounces as required by theUnited States Golf Association.

The following rubber compositions represent non-limiting examples ofpossible core formulations of the invention:

TABLE 1 INGREDIENTS (PHR) EX. 1 EX. 2 EX. 3 EX. 4 EX. 5 Polybutadiene100 100 100 100 100 rubber CTBN rubber — — — 5 10 Co-agent (ZDA) 25-3525-35 25-35 30 30 Zinc Oxide 5.0 5.0 5.0 5.0 5.0 ZnPCTP 0.3-0.7 0.3-0.70.3-0.7 0.6 0.6 Peroxide 0.5-1.3 0.5-1.3 0.5-1.3 1.5 1.5 Fortimix ® MC¹2.5 Fortimix ® HV¹ 3.0 Spherix ® 10¹ 3.0 2.5 2.5 Filler|Varied VariedVaried Varied Varied Varied ¹Fortimix ® MC, Fortimix ® HV andSpherix ® 10 are each functionalized inorganic aluminosilicate ceramicmicrospheres available from Spherix, Inc.

Advantageously, a golf ball of the invention includes rubbercompositions incorporating a plurality of functionalized inorganicaluminosilicate ceramic microspheres for adjusting important coreproperties such as CoR and/or spin by targeting cross-link density andspecific gravity/density, etc. without the agglomerating problem createdwhen using conventional additives/fillers for this purpose. Due at leastin part to the “ball bearing” effect of these microspheres, theuniformity of the spherical structure, collisions between themicrospheres during mixing, and the shear forces exerted on thematerials in the mixture, the microspheres may be uniformly dispersedthroughout the mixture—while functionalizations such as thiol, vinyl,methacrylate, epoxy, and carboxyl interact with the core formulation,thereby crosslinking to the polymer matrix permitting creation ofmodified rubber formulations having increased cross-link density and insome cases better hydrophobicity. That is, the inorganic aluminosilicateceramic microspheres contain organofunctional cure sites that bond tothe matrix rubber, increase rebound, reduce Tan Delta and lowercompression set.

These properties also help with consistency and process controlthroughout core mixing and molding and repeatability of such resultsreduces the need for processing aids and coating fillers in order to tryto address agglomeration associated with conventional fillers andmicrospheres which has continued to be a recurring problem in formingrubber-based core materials. An added benefit is that the functionalizedinorganic aluminosilicate ceramic microspheres are created with 100%post-industrial recycled mineral, which is an unusual property withinmany of the materials used in golf ball production.

In terms of functionality, the functionalized microspheres can crosslinkto the polymer matrix, which in turn can alter at will important golfball facets of the matrix using this novel approach. The functionalitymay be tailored to target and achieve a wide range of improvedrubber-based core materials. It was unexpected that these microspshereswould produce these results in golf ball materials without the need foradditional de-agglomeration processing aids or coating themicrospheres—and without meanwhile negatively impacting core propertiesand performance. Functionalizations such as thiol, vinyl, methacrylate,epoxy, and carboxyl can interact with the core formulation in differentways to produce additional cross-link density within the rubber-basedcore formulation matrix. The need for dispersants (i.e.,anti-agglomeration and/or anti-settling agents) in connection with thesemicrospheres is significantly reduced if not eliminated.

The term cross-link density, as used herein, is measure of crosslinkedpoints per unit volume of polymer (normally expressed in mol/m³).Cross-link density can be measured by solvent swelling measurements inaccordance to ASTM-D2765-95, method C utilizing a gravimetric method.Cross-link density may also be calculated by using a laser micrometer tomeasure the swell ratio of the polymer immersed in a solvent and thenheated, in accordance to a method developed by the Cambridge PolymerGroup, Inc. located in Somerville, Mass. One skilled in the art willunderstand that the presence and degree of crosslinking can also bedetermined by a variety of other methods, such as dynamic mechanicalthermal analysis (DMTA) in accordance with ASTM E1640-99.

In addition, the different levels of hydrophobicity of the various typesof functionalized inorganic aluminosilicate ceramic microspheres allowfor further customization of these additives for improving thehydrophobicity of the rubber core, which, being cross-linked withperoxide and/or zinc diacrylate, is adversely changed by moisture. Apolybutadiene core will absorb water and lose its resilience. Thus,these cores must be covered quickly to maintain optimum ball properties.And prolonged exposure to high humidity and elevated temperature may besufficient to allow water vapor to invade the cores of some commerciallyavailable golf balls. For example, at 110° F. and 90% humidity for asixty-day period, significant amounts of moisture enter the cores andreduce the initial velocity of the balls by 1.8 ft/s to 4.0 ft/s orgreater. The change in compression may vary from 5 PGA to about 10 PGAor greater. The absorbed water vapor also reduces the coefficient ofrestitution (CoR) of the ball.

To date, it has been difficult for golf ball manufacturers to improvethe hydrophobicity of the core material itself without meanwhilenegatively impacting important properties of the core, which in turnimpacts golf ball performance. Thus, moisture barrierfilms/layers/coatings or other outer golf ball layer materials aretypically used to protect the core from moisture penetration. In a golfball of the invention, functionalized inorganic aluminosilicate ceramicmicrospheres can be incorporated in at least one core layer, preferablythe outermost core layer, to further customize the core layerformulation to possess an improved normalized moisture vaportransmission rate compared with the same rubber composition without anyfunctionalized inorganic aluminosilicate ceramic microspheres.

In this regard, the core material's ability to resist moisturepenetration can be defined herein in terms of a normalized MVTR(nMVTR)(g·mm/m²·day)·(1/thickness (mm)) or g/(m² day)) which isirrespective of material thickness and permits a comparison of thenMVTRs of two given golf ball layers notwithstanding layer thickness.This is important because the inner core and outer core often havedifferent measurements. For example, the inner core can be relativelysmall in volume, for example, it may have a diameter within a range ofabout 0.10 to about 1.10 inches. More particularly, the inner core mayhave a diameter size with a lower limit of about 0.15 or 0.25 or 0.35 or0.45 or 0.55 inches and an upper limit of about 0.60 or 0.70 or 0.80 or0.90 inches. In one embodiment, the diameter of the inner core is in therange of about 0.025 to about 0.080 inches, more preferably about 0.030to about 0.075 inches. Meanwhile, the outer core layer may have athickness within a range of about 0.010 to about 0.250 inches. Forexample, the outer core may have a thickness with a lower limit of 0.010or 0.020 or 0.025 or 0.030 inches and an upper limit of 0.070 or 0.080or 0.100 or 0.200 inches. In one embodiment, the outer core layer has athickness in the range of about 0.040 to about 0.170 inches.

In a different embodiment, a golf ball of the invention comprises a coreand a cover; wherein the core comprises an inner core and an outer corelayer; the inner core comprising a first rubber composition, and theouter core layer comprising a second rubber composition; wherein onlyone of the first rubber composition and the second rubber compositionincludes a plurality of functionalized inorganic aluminosilicate ceramicmicrospheres dispersed throughout.

In a specific such embodiment, the second rubber composition of outercore layer includes the plurality of functionalized inorganicaluminosilicate ceramic microspheres and has a crosslink density that isgreater than a crosslink density of the first rubber composition of theinner core to create a positive crosslink density gradient from innercore to outer core layer. In particular such embodiments, the cross-linkdensity of the second core layer (mol/m³) may be greater than across-link density of the first core layer (mol/m³) by up to about 10%or by up to 10%, by at least 10%, or by at least 15%, or by at least25%, or by between about 10% and about 50%, or by up to about 50%, or byat least 50%, up to about 70% or by from about 40%-60%, or by up toabout 80%, or between about 50% and 85%, or between 50% and 75%, orbetween about 50% and about 75%.

Alternatively, in a different embodiment, a cross-link density gradientcan be created between a first core layer of a dual core and a secondcore layer of the dual core wherein the first core layer contains aplurality of functionalized inorganic aluminosilicate ceramicmicrospheres and the second core layer does not contain a plurality offunctionalized inorganic aluminosilicate ceramic microspheres. Inparticular such embodiments, the cross-link density of the second corelayer (mol/m³) may be less than a cross-link density of the first corelayer (mol/m³) by up to about 10% or by up to 10%, by at least 10%, orby at least 15%, or by at least 25%, or by between about 10% and about50%, or by up to about 50%, or by at least 50%, up to about 70% or byfrom about 40%-60%, or by up to about 80%, or between about 50% and 85%,or between 50% and 75%, or between about 50% and about 75%.

In some embodiments, there may be a nMVTR gradient between the corelayers wherein the nMVTR of the second core layer is greater than annMVTR of the first core layer, or vice vera. In such embodiments, thefirst core layer may be an inner core layer while the second core layeris an outer core layer, or vice versa.

In a preferred embodiment, the second rubber composition of the outercore layer has a greater nMVTR than an nMVTR of the first rubbercomposition of the inner core to create a positive nMVTR gradient frominner core to outer core layer.

In yet another embodiment, a golf ball of the invention comprises a coreand a cover, wherein the core comprises an inner core and an outer corelayer; wherein the inner core comprises a first rubber compositionincluding a first plurality of functionalized inorganic aluminosilicateceramic microspheres dispersed throughout; wherein the outer core layercomprises a second rubber composition including a second plurality offunctionalized inorganic aluminosilicate ceramic microspheres dispersedthroughout; wherein the first rubber composition and the second rubbercomposition differ at least in that the first plurality and the secondplurality differ as to at least one of: (i) amount of functionalizedinorganic aluminosilicate ceramic microspheres included in each of thefirst rubber composition and the second rubber composition, in parts perhundred, based on 100 phr of polybutadiene contained in the rubbercomposition; and/or (ii) type(s) of functionalized inorganicaluminosilicate ceramic microspheres included in each of the firstrubber composition and the second rubber composition; and/or (iii)degree of functionalization of the functionalized inorganicaluminosilicate ceramic microsphere included in each of the first rubbercomposition and the second rubber composition.

Thus, in one specific embodiment, a golf ball of the invention comprisesa dual core comprised of a spherical inner core and an outer core layer,wherein each of the spherical inner core and the outer core layercomprises the same rubber-based composition but the amount offunctionalized inorganic aluminosilicate ceramic microspheres (phr per100 phr of polybutadiene) dispersed throughout the rubber-basedcomposition of the outer core layer is greater than the amount (phr per100 phr of polybutadiene) of functionalized inorganic aluminosilicateceramic microspheres dispersed throughout the rubber-based compositionof the spherical inner core to create and define a positive cross-linkdensity gradient from the spherical inner core to the outer core layer.

In a different specific embodiment, a golf ball of the inventioncomprises a dual core comprised of a spherical inner core and an outercore layer, wherein each of the spherical inner core and the outer corelayer comprises the same rubber-based composition but the amount offunctionalized inorganic aluminosilicate ceramic microspheres (phr per100 phr of polybutadiene) dispersed throughout the rubber-basedcomposition of the spherical inner core is greater than the amount (phrper 100 phr of polybutadiene) of functionalized inorganicaluminosilicate ceramic microspheres dispersed throughout therubber-based composition of the outer core layer to create and define anegative cross-link density gradient from the spherical inner core tothe outer core layer.

In yet another specific embodiment, a golf ball of the inventioncomprises a dual core comprised of a spherical inner core and an outercore layer, wherein each of the spherical inner core and the outer corelayer comprises the same rubber-based composition but the type offunctionalized inorganic aluminosilicate ceramic microspheres dispersedthroughout the rubber-based composition of the outer core layer isdifferent than the type of functionalized inorganic aluminosilicateceramic microspheres dispersed throughout the rubber-based compositionof the spherical inner core to define one of a positive or negative across-link density gradient between spherical inner core and outer corelayer, depending on the pre-selected functionalized inorganicaluminosilicate ceramic microspheres dispersed throughout each corelayer.

In particular such embodiments, the first plurality of functionalizedinorganic aluminosilicate ceramic microspheres may be selected fromthiol-functionalized, vinyl-functionalized, methacrylate-functionalized,acrylate-functionalized epoxy-functionalized, and/orcarboxyl-functionalized; and the different second functionalizedinorganic aluminosilicate ceramic microspheres are also selected fromthiol-functionalized, vinyl-functionalized, methacrylate-functionalized,acrylate-functionalized, epoxy-functionalized, and/orcarboxyl-functionalized inorganic aluminosilicate ceramic microspheres.

In still another specific embodiment, a golf ball of the inventioncomprises a dual core comprised of a spherical inner core and an outercore layer, wherein each of the spherical inner core and the outer corelayer comprises the same rubber-based composition but the degree offunctionalization of the functionalized inorganic aluminosilicateceramic microspheres dispersed throughout the rubber-based compositionof the outer core layer is different than the degree offunctionalization of the functionalized inorganic aluminosilicateceramic microspheres dispersed throughout the rubber-based compositionof the spherical inner core to define one of a positive or negative across-link density gradient between spherical inner core and outer corelayer, depending on the pre-selected functionalized inorganicaluminosilicate ceramic microspheres dispersed throughout each corelayer.

In particular such embodiments, the first plurality of functionalizedinorganic aluminosilicate ceramic microspheres are at least one ofthiol-functionalized, vinyl-functionalized, methacrylate-functionalized,acrylate-functionalized epoxy-functionalized, and/orcarboxyl-functionalized; and the second functionalized inorganicaluminosilicate ceramic microspheres are differently functionalizedthiol-functionalized, vinyl-functionalized, methacrylate-functionalized,acrylate-functionalized, epoxy-functionalized, and/orcarboxyl-functionalized inorganic aluminosilicate ceramic microspheres.

In each of these examples, the overall CoR of cores of the presentinvention at 125 ft/s is at least 0.750, or at least 0.775, or at least0.760, or at least 0.077, or at least 0.780, or at least 0.785, or atleast 0.790, or at least 0.795, or at least 0.800, or at least 0.810. Agolf ball having a CoR value closer to 1 will generally correspond to agolf ball having a higher initial velocity and a greater overalldistance. In general, a higher compression core will result in a higherCoR value, and therefore increasing the cross-linking density of one ormore core layers will raise the compression of the core as well.

In golf balls of the invention, cross-link density gradients may becreated between core layers by pre-electing the presence/absence,amount, type, and degree of functionalization of the plurality offunctionalized inorganic aluminosilicate ceramic microspheres in twogiven core layers to target important properties such as resilience/CoRand desired playing characteristics such as distance.

The diameter and thickness of the different layers along with propertiessuch as hardness and compression may vary depending upon theconstruction and desired playing performance properties of the golf ballas discussed further below. Golf balls of the invention may thereforehave any number of layers, with the one limitation being that at leastone layer of the golf ball, preferably a thermoset rubber core layer,includes a plurality of functionalized inorganic aluminosilicate ceramicmicrospheres dispersed throughout as disclosed and described herein.Thus, while a golf ball of the invention may include a dual coreconstruction, embodiments are indeed envisioned wherein the core hasthree or more layers. For example, the core may comprise a sphericalinner core, and intermediate core layer that surrounds and is adjacentto the spherical inner core, and an outer core layer that is disposedabout the intermediate core layer. In such embodiments, it is envisionedthat any one or more of these core layers may include a plurality offunctionalized inorganic aluminosilicate ceramic microspheres, and thatany two or more of these core layers can vary the presence/absence,amount, type, and degree of functionalization of the plurality offunctionalized inorganic aluminosilicate ceramic microspheres to createcross-link density gradients therebetween to target important propertiessuch as resilience/CoR and desired playing characteristics such asdistance.

Furthermore, embodiments are indeed also envisioned wherein a layer ofthe golf ball other than a core layer includes a plurality offunctionalized inorganic aluminosilicate ceramic microspheresthroughout. For example, in some embodiments an intermediate layer or acover layer may include a plurality of functionalized inorganicaluminosilicate ceramic microspheres throughout to target golf ballplaying characteristics.

Thus, as used herein the term, “layer” means generally any sphericalportion of the golf ball. It is contemplated that a resulting golf ballof the invention is at least a two-piece golf ball including at leastone core layer and at least one cover layer.

In one embodiment, the core may have a diameter ranging from about 0.09inches to about 1.65 inches, or up to about 1.70 inches, or greater than1.70 inches. In one embodiment, the diameter of the core of the presentinvention is about 1.2 inches to about 1.630 inches. When part of atwo-piece ball according to invention, the core may have a diameterranging from about 1.5 inches to about 1.62 inches. In anotherembodiment, the diameter of the core is about 1.3 inches to about 1.6inches, preferably from about 1.39 inches to about 1.6 inches, and morepreferably from about 1.5 inches to about 1.6 inches. In yet anotherembodiment, the core has a diameter of about 1.55 inches to about 1.65inches, preferably about 1.55 inches to about 1.60 inches.

In some embodiments, the core may have an overall diameter within arange having a lower limit of 0.500 or 0.700 or 0.750 or 0.800 or 0.850or 0.900 or 0.950 or 1.000 or 1.100 or 1.150 or 1.200 or 1.250 or 1.300or 1.350 or 1.400 or 1.450 or 1.500 or 1.600 or 1.610 inches and anupper limit of 1.620 or 1.630 or 1.640 inches. In a particularembodiment, the core is a multi-layer core having an overall diameterwithin a range having a lower limit of 0.500 or 0.700 or 0.750 or 0.800or 0.850 or 0.900 or 0.950 or 1.000 or 1.100 or 1.150 or 1.200 inchesand an upper limit of 1.250 or 1.300 or 1.350 or 1.400 or 1.450 or 1.500or 1.600 or 1.610 or 1.620 or 1.630 or 1.640 inches. In anotherparticular embodiment, the multi-layer core has an overall diameterwithin a range having a lower limit of 0.500 or 0.700 or 0.750 inchesand an upper limit of 0.800 or 0.850 or 0.900 or 0.950 or 1.000 or 1.100or 1.150 or 1.200 or 1.250 or 1.300 or 1.350 or 1.400 or 1.450 or 1.500or 1.600 or 1.610 or 1.620 or 1.630 or 1.640 inches. In anotherparticular embodiment, the multi-layer core has an overall diameter of1.500 inches or 1.510 inches or 1.530 inches or 1.550 inches or 1.570inches or 1.580 inches or 1.590 inches or 1.600 inches or 1.610 inchesor 1.620 inches.

In some embodiments, the inner core can have an overall diameter of0.500 inches or greater, or 0.700 inches or greater, or 1.00 inches orgreater, or 1.250 inches or greater, or 1.350 inches or greater, or1.390 inches or greater, or 1.450 inches or greater, or an overalldiameter within a range having a lower limit of 0.250 or 0.500 or 0.750or 1.000 or 1.250 or 1.350 or 1.390 or 1.400 or 1.440 inches and anupper limit of 1.460 or 1.490 or 1.500 or 1.550 or 1.580 or 1.600inches, or an overall diameter within a range having a lower limit of0.250 or 0.300 or 0.350 or 0.400 or 0.500 or 0.550 or 0.600 or 0.650 or0.700 inches and an upper limit of 0.750 or 0.800 or 0.900 or 0.950 or1.000 or 1.100 or 1.150 or 1.200 or 1.250 or 1.300 or 1.350 or 1.400inches.

In some embodiments, the outer core layer can have an overall thicknesswithin a range having a lower limit of 0.010 or 0.020 or 0.025 or 0.030or 0.035 inches and an upper limit of 0.040 or 0.070 or 0.075 or 0.080or 0.100 or 0.150 inches, or an overall thickness within a range havinga lower limit of 0.025 or 0.050 or 0.100 or 0.150 or 0.160 or 0.170 or0.200 inches and an upper limit of 0.225 or 0.250 or 0.275 or 0.300 or0.325 or 0.350 or 0.400 or 0.450 or greater than 0.450 inches. The outercore layer may alternatively have a thickness of greater than 0.10inches, or 0.20 inches or greater, or greater than 0.20 inches, or 0.30inches or greater, or greater than 0.30 inches, or 0.35 inches orgreater, or greater than 0.35 inches, or 0.40 inches or greater, orgreater than 0.40 inches, or 0.45 inches or greater, or greater than0.45 inches, or a thickness within a range having a lower limit of 0.005or 0.010 or 0.015 or 0.020 or 0.025 or 0.030 or 0.035 or 0.040 or 0.045or 0.050 or 0.055 or 0.060 or 0.065 or 0.070 or 0.075 or 0.080 or 0.090or 0.100 or 0.200 or 0.250 inches and an upper limit of 0.300 or 0.350or 0.400 or 0.450 or 0.500 or 0.750 inches.

An intermediate core layer can have any known overall thickness such aswithin a range having a lower limit of 0.005 or 0.010 or 0.015 or 0.020or 0.025 or 0.030 or 0.035 or 0.040 or 0.045 inches and an upper limitof 0.050 or 0.055 or 0.060 or 0.065 or 0.070 or 0.075 or 0.080 or 0.090or 0.100 inches.

The compression of the core is generally overall in the range of about40 to about 110, although embodiments are envisioned wherein thecompression of the core is as low as 5. In other embodiments, theoverall CoR of cores of the present invention at 125 ft/s is at least0.750, or at least 0.775 or at least 0.780, or at least 0.785, or atleast 0.790, or at least 0.795, or at least 0.800. While at least onecore layer is preferably comprised of rubber, a core layer may also beformed of a variety of other materials that are typically also used forintermediate and cover layers.

The cores and core layers of golf balls of the invention may havevarying hardnesses depending on the particular golf ball constructionand playing characteristics being targeted. Core center and/or layerhardness can range, for example, from 35 Shore C to about 98 Shore C, or50 Shore C to about 90 Shore C, or 60 Shore C to about 85 Shore C, or 45Shore C to about 75 Shore C, or 40 Shore C to about 85 Shore C. In otherembodiments, core center and/or layer hardness can range, for example,from about 20 Shore D to about 78 Shore D, or from about 30 Shore D toabout 60 Shore D, or from about 40 Shore D to about 50 Shore D, or 50Shore D or less, or greater than 50 Shore D.

The inner core preferably has a geometric center hardness(H_(inner core center)) of about 5 Shore D or greater. For example, the(H_(inner core center)) may be in the range of about 5 to about 88 ShoreD and more particularly within a range having a lower limit of about 5or 10 or 18 or 20 and an upper limit of about 80 or 82 or 84 or 88 ShoreD.

In another example, the center hardness of the inner core(H_(inner core center)), as measured in Shore C units, is preferablyabout 10 Shore C or greater; for example, the H_(inner core center) mayhave a lower limit of about 10 or 14 or 16 or 20 and an upper limit ofabout 78 or 80 or 84 or 90 Shore C. Concerning the outer surfacehardness of the inner core (H_(inner core surface)), this hardness ispreferably about 12 Shore D or greater; for example, theH_(inner core surface) may fall within a range having a lower limit ofabout 12 or 15 or 18 or 20 and an upper limit of about 80 or 84 or 86 or90 Shore D. In one version, the outer surface hardness of the inner core(H_(inner core surface)), as measured in Shore C units, has a lowerlimit of about 13 or 15 or 18 or 20 and an upper limit of about 86 or 88or 90 or 92 Shore C. In another version, the geometric center hardness(H_(inner core) center) is in the range of about 10 Shore C to about 50Shore C; and the outer surface hardness of the inner core(H_(inner core surface)) is in the range of about 5 Shore C to about 50Shore C.

On the other hand, the outer core layer preferably has an outer surfacehardness (H_(outer surface of OC)) of about 40 Shore D or greater, andmore preferably within a range having a lower limit of about 40 or 42 or44 or 46 and an upper limit of about 85 or 87 or 88 or 90 Shore D. Theouter surface hardness of the outer core layer(H_(outer surface of OC)), as measured in Shore C units, preferably hasa lower limit of about 40 or 42 or 45 or 48 and an upper limit of about88 or 90 or 92 or 95 Shore C.

And, the midpoint hardness of the outer core layer (H_(midpoint of OC))preferably has a hardness of about 40 Shore D or greater, and morepreferably within a range having a lower limit of about 40 or 42 or 46or 48 or 50 and an upper limit of about 80 or 82 or 85 or 88 or 90 ShoreD. The midpoint hardness of the outer core layer (H_(midpoint of OC)),as measured in Shore C units, preferably has a lower limit of about 40or 42 or 44 or 45 or 47 and an upper limit of about 85 or 88 or 90 or 92or 95 Shore C.

The midpoint of a layer is taken at a point equidistant from the innersurface and outer surface of the layer to be measured, most typically anouter core layer. Once one or more core layers surround a layer ofinterest, the exact midpoint may be difficult to determine, therefore,for the purposes of the present invention, the measurement of “midpoint”hardness of a layer is taken within plus or minus 1 mm of the measuredmidpoint of the layer.

The hardness of the core sub-assembly (inner core and outer core layer)is an important property. In one preferred golf ball, the inner core(center) has a “positive” hardness gradient (that is, the outer surfaceof the inner core is harder than its geometric center); and the outercore layer has a “positive” hardness gradient (that is, the outersurface of the outer core layer is harder than the inner surface of theouter core layer.) In such cases where both the inner core and outercore layer each has a “positive” hardness gradient, the outer surfacehardness of the outer core layer is preferably greater than the hardnessof the geometric center of the inner core.

In an alternative version, the inner core may have a positive hardnessgradient; and the outer core layer may have a “zero” hardness gradient(that is, the hardness values of the outer surface of the outer corelayer and the inner surface of the outer core layer are substantiallythe same) or a “negative” hardness gradient (that is, the outer surfaceof the outer core layer is softer than the inner surface of the outercore layer.) In a second alternative version, the inner core may have azero or negative hardness gradient; and the outer core layer may have apositive hardness gradient. Still yet, in another embodiment, both theinner core and outer core layers have zero or negative hardnessgradients.

The core layers have positive, negative, or zero hardness gradientsdefined by hardness measurements made at the outer surface of the innercore (or outer surface of the outer core) and radially inward towardsthe center of the inner core (or inner surface or midpoint of the outercore). These measurements are made typically at 2-mm increments asdescribed in the test methods below. In general, the hardness gradientis determined by subtracting the hardness value at the innermost portionof the component being measured (for example, the center of the innercore or inner surface or midpoint of the intermediate layer) from thehardness value at the outer surface of the component being measured (forexample, the outer surface of the inner core or outer surface of theintermediate layer).

The core structure also may have a hardness gradient across the entirecore assembly. In one embodiment, the (H_(inner core center)) is in therange of about 10 Shore C to about 60 Shore C, preferably about 13 ShoreC to about 55 Shore C; and the (H_(outer surface of OC)) is in the rangeof about 65 to about 96 Shore C, preferably about 68 Shore C to about 94Shore C to provide a positive hardness gradient across the coreassembly.

In another embodiment, there is a zero or negative hardness gradientacross the core assembly. For example, the center of the core(H_(inner core center)) may have a hardness in the range of 20 to 90Shore C; and the outer surface of the outer core may have a hardness inthe range of 10 to 80 Shore C.

The hardness gradient across the core assembly will vary based onseveral factors including, but not limited to, the dimensions of theinner core, any intermediate core layer, and outer core layer(s).

Examples of suitable core compositions include rubber materials such aspolybutadiene, ethylene-propylene rubber, ethylene-propylene-dienerubber, polyisoprene, styrene-butadiene rubber, polyalkenamers, butylrubber, halobutyl rubber, and/or polystyrene elastomers.

In general, polybutadiene is a homopolymer of 1, 3-butadiene. The doublebonds in the 1, 3-butadiene monomer are attacked by catalysts to growthe polymer chain and form a polybutadiene polymer having a desiredmolecular weight. Any suitable catalyst may be used to synthesize thepolybutadiene rubber depending upon the desired properties. Normally, atransition metal complex (for example, neodymium, nickel, or cobalt) oran alkyl metal such as alkyllithium is used as a catalyst. Othercatalysts include, but are not limited to, aluminum, boron, lithium,titanium, and combinations thereof. The catalysts produce polybutadienerubbers having different chemical structures.

In a cis-bond configuration, the main internal polymer chain of thepolybutadiene appears on the same side of the carbon-carbon double bondcontained in the polybutadiene. In a trans-bond configuration, the maininternal polymer chain is on opposite sides of the internalcarbon-carbon double bond in the polybutadiene. The polybutadiene rubbercan have various combinations of cis- and trans-bond structures.

A preferred polybutadiene rubber has a 1,4 cis-bond content of at least40%, preferably greater than 80%, and more preferably greater than 90%.In general, polybutadiene rubbers having a high 1,4 cis-bond contenthave high tensile strength. The polybutadiene rubber may have arelatively high or low Mooney viscosity.

Examples of commercially-available polybutadiene rubbers that can beused in accordance with this invention, include, but are not limited to,BR 01 and BR 1220, available from BST Elastomers of Bangkok, Thailand;SE BR 1220LA and SE BR1203, available from DOW Chemical Co of Midland,Mich.; BUDENE 1207, 1207s, 1208, and 1280 available from Goodyear, Incof Akron, Ohio; BR 01, 51 and 730, available from Japan Synthetic Rubber(JSR) of Tokyo, Japan; BUNA CB 21, CB 22, CB 23, CB 24, CB 25, CB 29MES, CB 60, CB Nd 60, CB 55 NF, CB 70 B, CB KA 8967, and CB 1221,available from Lanxess Corp. of Pittsburgh. Pa.; BR1208, available fromLG Chemical of Seoul, South Korea; UBEPOL BR130B, BR150, BR150B, BR150L,BR230, BR360L, BR710, and VCR617, available from UBE Industries, Ltd. ofTokyo, Japan; EUROPRENE NEOCIS BR 60, INTENE 60 AF and P30AF, andEUROPRENE BR HV80, available from Polimeri Europa of Rome, Italy; AFDENE50 and NEODENE BR40, BR45, BR50 and BR60, available from Karbochem (PTY)Ltd. of Bruma, South Africa; KBR 01, NdBr 40, NdBR-45, NdBr 60, KBR710S, KBR 710H, and KBR 750, available from Kumho Petrochemical Co.,Ltd. Of Seoul, South Korea; and DIENE 55NF, 70AC, and 320 AC, availablefrom Firestone Polymers of Akron, Ohio.

To form the core, the polybutadiene rubber is used in an amount of atleast about 5% by weight based on total weight of composition and isgenerally present in an amount of about 5% to about 100%, or an amountwithin a range having a lower limit of 5% or 10% or 20% or 30% or 40% or50% and an upper limit of 55% or 60% or 70% or 80% or 90% or 95% or100%. In general, the concentration of polybutadiene rubber is about 45to about 95 weight percent. Preferably, the rubber material used to formthe core layer comprises at least 50% by weight, and more preferably atleast 70% by weight, polybutadiene rubber.

The rubber compositions of this invention may be peroxide-cured withoutinhibiting cure. Suitable organic peroxides include, but are not limitedto, dicumyl peroxide; n-butyl-4,4-di(t-butylperoxy) valerate;1,1-di(t-butylperoxy)3,3,5-trimethylcyclohexane;2,5-dimethyl-2,5-di(t-butylperoxy) hexane; di-t-butyl peroxide;di-t-amyl peroxide; t-butyl peroxide; t-butyl cumyl peroxide;2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3;di(2-t-butyl-peroxyisopropyl)benzene; dilauroyl peroxide; dibenzoylperoxide; t-butyl hydroperoxide; and combinations thereof. In aparticular embodiment, the free radical initiator is dicumyl peroxide,including, but not limited to Perkadox® BC, commercially available fromAkzo Nobel.

Peroxide free-radical initiators are generally present in the rubbercomposition in an amount of at least 0.05 parts by weight per 100 partsof the total rubber, or an amount within the range having a lower limitof 0.05 parts or 0.1 parts or 1 part or 1.25 parts or 1.5 parts or 2.5parts or 5 parts by weight per 100 parts of the total rubbers, and anupper limit of 2.5 parts or 3 parts or 5 parts or 6 parts or 10 parts or15 parts by weight per 100 parts of the total rubber. Concentrations arein parts per hundred (phr) unless otherwise indicated. As used herein,the term, “parts per hundred,” also known as “phr” or “pph” is definedas the number of parts by weight of a particular component present in amixture, relative to 100 parts by weight of the polymer component.Mathematically, this can be expressed as the weight of an ingredientdivided by the total weight of the polymer, multiplied by a factor of100.

Suitable co-agents, where desired, may include, but are not limited to,metal salts of unsaturated carboxylic acids having from 3 to 8 carbonatoms; unsaturated vinyl compounds and polyfunctional monomers (e.g.,trimethylolpropane trimethacrylate); phenylene bismaleimide; andcombinations thereof. Particular examples of suitable metal saltsinclude, but are not limited to, one or more metal salts of acrylates,diacrylates, methacrylates, and dimethacrylates, wherein the metal isselected from magnesium, calcium, zinc, aluminum, lithium, and nickel.In a particular embodiment, the co-agent is selected from zinc salts ofacrylates, diacrylates, methacrylates, and dimethacrylates.

In another particular embodiment, the agent is zinc diacrylate (ZDA).When the co-agent is zinc diacrylate and/or zinc dimethacrylate, theco-agent is typically included in the rubber composition in an amountwithin the range having a lower limit of 1 or 5 or 10 or 15 or 19 or 20parts by weight per 100 parts of the total rubber, and an upper limit of24 or 25 or 30 or 35 or 40 or 45 or 50 or 60 parts by weight per 100parts of the base rubber.

Radical scavengers such as a halogenated organosulfur or metal saltthereof, organic disulfide, or inorganic disulfide compounds may beadded to the rubber composition. These compounds also may function as“soft and fast agents.” As used herein, “soft and fast agent” means anycompound or a blend thereof that is capable of making a core: 1) softer(having a lower compression) at a constant “coefficient of restitution”(COR); and/or 2) faster (having a higher COR at equal compression), whencompared to a core equivalently prepared without a soft and fast agent.

Preferred halogenated organosulfur compounds include, but are notlimited to, pentachlorothiophenol (PCTP) and salts of PCTP such as zincpentachlorothiophenol (ZnPCTP). Using PCTP and ZnPCTP in golf ball innercores helps produce softer and faster inner cores. The PCTP and ZnPCTPcompounds help increase the resiliency and the coefficient ofrestitution of the core. In a particular embodiment, the soft and fastagent is selected from ZnPCTP, PCTP, ditolyl disulfide, diphenyldisulfide, dixylyl disulfide, 2-nitroresorcinol, and combinationsthereof.

The rubber compositions of the present invention also may include other“fillers,” which are added to adjust the density and/or specific gravityof the material. Suitable fillers include, but are not limited to,polymeric or mineral fillers, metal fillers, metal alloy fillers, metaloxide fillers and carbonaceous fillers. The fillers can be in anysuitable form including, but not limited to, flakes, fibers, whiskers,fibrils, plates, particles, and powders. Rubber regrind, which isground, recycled rubber material (for example, ground to about 30 meshparticle size) obtained from discarded rubber golf ball cores, also canbe used as a filler. The amount and type of fillers utilized aregoverned by the amount and weight of other ingredients in the golf ball,since a maximum golf ball weight of 45.93 g (1.62 ounces) has beenestablished by the United States Golf Association (USGA).

Suitable polymeric or mineral fillers that may be added to the rubbercomposition include, for example, precipitated hydrated silica, clay,talc, asbestos, glass fibers, aramid fibers, mica, calcium metasilicate,barium sulfate, zinc sulfide, lithopone, silicates, silicon carbide,tungsten carbide, diatomaceous earth, polyvinyl chloride, carbonatessuch as calcium carbonate and magnesium carbonate. Suitable metalfillers include titanium, tungsten, aluminum, bismuth, nickel,molybdenum, iron, lead, copper, boron, cobalt, beryllium, zinc, and tin.Suitable metal alloys include steel, brass, bronze, boron carbidewhiskers, and tungsten carbide whiskers. Suitable metal oxide fillersinclude zinc oxide, iron oxide, aluminum oxide, titanium oxide,magnesium oxide, and zirconium oxide. Suitable particulate carbonaceousfillers include graphite, carbon black, cotton flock, natural bitumen,cellulose flock, and leather fiber. Micro balloon fillers such as glassand ceramic, and fly ash fillers can also be used.

In a particular aspect of this embodiment, the rubber compositionincludes filler(s) selected from carbon black, nanoclays (e.g.,Cloisite® and Nanofil® nanoclays, commercially available from SouthernClay Products, Inc., and Nanomax® and Nanomer® nanoclays, commerciallyavailable from Nanocor, Inc.), talc (e.g., Luzenac HAR® high aspectratio talcs, commercially available from Luzenac America, Inc.), glass(e.g., glass flake, milled glass, and microglass), mica and mica-basedpigments (e.g., Iriodin® pearl luster pigments, commercially availablefrom The Merck Group), and combinations thereof. In a particularembodiment, the rubber composition is modified with organic fibermicropulp.

In addition, the rubber compositions may include antioxidants to preventthe breakdown of the elastomers. Also, processing aids such as highmolecular weight organic acids and salts thereof, may be added to thecomposition. In a particular embodiment, the total amount of additive(s)and filler(s) present in the rubber composition is 15 wt % or less, or12 wt % or less, or 10 wt % or less, or 9 wt % or less, or 6 wt % orless, or 5 wt % or less, or 4 wt % or less, or 3 wt % or less, based onthe total weight of the rubber composition.

The polybutadiene rubber material (base rubber) may be blended withother elastomers in accordance with this invention. Other elastomersinclude, but are not limited to, polybutadiene, polyisoprene, ethylenepropylene rubber (“EPR”), styrene-butadiene rubber, styrenic blockcopolymer rubbers (such as “SI”, “SIS”, “SB”, “SBS”, “SIBS”, and thelike, where “S” is styrene, “I” is isobutylene, and “B” is butadiene),polyalkenamers such as, for example, polyoctenamer, butyl rubber,halobutyl rubber, polystyrene elastomers, polyethylene elastomers,polyurethane elastomers, polyurea elastomers, metallocene-catalyzedelastomers and plastomers, copolymers of isobutylene and p-alkylstyrene,halogenated copolymers of isobutylene and p-alkylstyrene, copolymers ofbutadiene with acrylonitrile, polychloroprene, alkyl acrylate rubber,chlorinated isoprene rubber, acrylonitrile chlorinated isoprene rubber,and combinations of two or more thereof.

For example, in one embodiment, the elastomer composition may comprisei) about 50% to about 95% by weight of a non-metallocene catalyzedpolybutadiene rubber; and ii) about 5 to about 50% by weight of ametallocene-catalyzed polybutadiene rubber; wherein examples of suitablenon-metallocene catalysts (may be referred to as Ziegler-Nattacatalysts) include neodymium, nickel, cobalt, titanium, aluminum, boron,and alkylithium-based catalysts, and combinations thereof; and examplesof suitable metallocene catalysts are complexes based on metals such ascobalt, gadolinium, iron, lanthanum, neodymium, nickel, praseodymium,samarium, titanium, vanadium, zirconium; and combinations thereof.

The polymers, free-radical initiators, filler, cross-linking agents, andany other materials used in forming either the golf ball center or anyof the core, in accordance with invention, may be combined to form amixture by any type of mixing known to one of ordinary skill in the art.Suitable types of mixing include single pass and multi-pass mixing, andthe like. The cross-linking agent, and any other optional additives usedto modify the characteristics of the golf ball center or additionallayer(s), may similarly be combined by any type of mixing.

A single-pass mixing process where ingredients are added sequentially ispreferred, as this type of mixing tends to increase efficiency andreduce costs for the process. The preferred mixing cycle is single stepwherein the polymer, cis-to-trans catalyst, filler, zinc diacrylate, andperoxide are added in sequence.

In preferred embodiments, at least one core layer is formed of a rubbercomposition comprising a material selected from the group of natural andsynthetic rubbers including, but not limited to, polybutadiene,polyisoprene, ethylene propylene rubber (“EPR”),ethylene-propylene-diene (“EPDM”) rubber, styrene-butadiene rubber,styrenic block copolymer rubbers (such as “SI”, “SIS”, “SB”, “SBS”,“SIBS”, and the like, where “S” is styrene, “I” is isobutylene, and “B”is butadiene), polyalkenamers such as, for example, polyoctenamer, butylrubber, halobutyl rubber, polystyrene elastomers, polyethyleneelastomers, polyurethane elastomers, polyurea elastomers,metallocene-catalyzed elastomers and plastomers, copolymers ofisobutylene and p-alkylstyrene, halogenated copolymers of isobutyleneand p-alkylstyrene, copolymers of butadiene with acrylonitrile,polychloroprene, alkyl acrylate rubber, chlorinated isoprene rubber,acrylonitrile chlorinated isoprene rubber, and combinations of two ormore thereof.

The core structure may be surface-treated to increase the adhesionbetween its outer surface and the next layer that will be applied overthe core. Such surface-treatment may include mechanically orchemically-abrading the outer surface of the core. For example, the coremay be subjected to corona-discharge, plasma-treatment, silane-dipping,or other treatment methods known to those in the art.

Additionally, property gradients can be created between golf ball corelayers by varying the type and/or relative amounts of peroxide used intwo given layers.

Polyurethanes are also suitable materials for golf ball layers. Ingeneral, polyurethanes contain urethane linkages formed by reacting anisocyanate group (—N═C═O) with a hydroxyl group (OH). The polyurethanesare produced by the reaction of a multi-functional isocyanate(NCO—R—NCO) with a long-chain polyol having terminal hydroxyl groups(OH—OH) in the presence of a catalyst and other additives. The chainlength of the polyurethane prepolymer is extended by reacting it withshort-chain diols (OH—R′—OH). The resulting polyurethane has elastomericproperties because of its “hard” and “soft” segments, which arecovalently bonded together. This phase separation occurs because themainly non-polar, low melting soft segments are incompatible with thepolar, high melting hard segments. The hard segments, which are formedby the reaction of the diisocyanate and low molecular weightchain-extending diol, are relatively stiff and immobile. The softsegments, which are formed by the reaction of the diisocyanate and longchain diol, are relatively flexible and mobile. Because the hardsegments are covalently coupled to the soft segments, they inhibitplastic flow of the polymer chains, thus creating elastomericresiliency.

By the term, “isocyanate compound” as used herein, it is meant anyaliphatic or aromatic isocyanate containing two or more isocyanatefunctional groups. The isocyanate compounds can be monomers or monomericunits, because they can be polymerized to produce polymeric isocyanatescontaining two or more monomeric isocyanate repeat units. The isocyanatecompound may have any suitable backbone chain structure includingsaturated or unsaturated, and linear, branched, or cyclic. By the term,“polyamine” as used herein, it is meant any aliphatic or aromaticcompound containing two or more primary or secondary amine functionalgroups. The polyamine compound may have any suitable backbone chainstructure including saturated or unsaturated, and linear, branched, orcyclic. The term “polyamine” may be used interchangeably withamine-terminated component. By the term, “polyol” as used herein, it ismeant any aliphatic or aromatic compound containing two or more hydroxylfunctional groups. The term “polyol” may be used interchangeably withhydroxy-terminated component.

Thermoplastic polyurethanes have minimal cross-linking; any bonding inthe polymer network is primarily through hydrogen bonding or otherphysical mechanism. Because of their lower level of cross-linking,thermoplastic polyurethanes are relatively flexible. The cross-linkingbonds in thermoplastic polyurethanes can be reversibly broken byincreasing temperature such as during molding or extrusion. That is, thethermoplastic material softens when exposed to heat and returns to itsoriginal condition when cooled.

Thermoplastic polyurethanes are therefore particularly desirable as anouter cover layer material. Non-limiting examples of suitablethermoplastic polyurethanes include TPUs sold under the tradenames ofTexin® 250, Texin® 255, Texin® 260, Texin® 270, Texin®950U, Texin® 970U,Texin® 1049, Texin® 990DP7-1191, Texin® DP7-1202, Texin®990R, Texin®993,Texin®DP7-1049, Texin® 3203, Texin® 4203, Texin® 4206, Texin® 4210,Texin® 4215, and Texin® 3215, each commercially available from CovestroLLC, Pittsburgh Pa.; Estane® 50 DT3, Estane®58212, Estane®55DT3,Estane®58887, Estane®EZ14-23A, Estane®ETE 50DT3, each commerciallyavailable from Lubrizol Company of Cleveland, Ohio; andElastollan®WY1149, Elastollan®1154D53, Elastollan®1180A,Elastollan®1190A, Elastollan®1195A, Elastollan®1185AW,Elastollan®1175AW, each commercially available from BASF; Desmopan® 453,commercially available from Bayer of Pittsburgh, Pa., and the E-SeriesTPUs, such as D 60 E 4024 commercially available from HuntsmanPolyurethanes of Germany.

On the other hand, thermoset polyurethanes become irreversibly set whenthey are cured. The cross-linking bonds are irreversibly set and are notbroken when exposed to heat. Thus, thermoset polyurethanes, whichtypically have a high level of cross-linking, are relatively rigid.

Aromatic polyurethanes can be prepared in accordance with this inventionand these materials are preferably formed by reacting an aromaticdiisocyanate with a polyol. Suitable aromatic diisocyanates that may beused in accordance with this invention include, for example, toluene2,4-diisocyanate (TDI), toluene 2,6-diisocyanate (TDI), 4,4′-methylenediphenyl diisocyanate (MDI), 2,4′-methylene diphenyl diisocyanate (MDI),polymeric methylene diphenyl diisocyanate (PMDI), p-phenylenediisocyanate (PPDI), m-phenylene diisocyanate (PDI), naphthalene1,5-diisocynate (NDI), naphthalene 2,4-diisocyanate (NDI), p-xylenediisocyanate (XDI), and homopolymers and copolymers and blends thereof.The aromatic isocyanates are able to react with the hydroxyl or aminecompounds and form a durable and tough polymer having a high meltingpoint. The resulting polyurethane generally has good mechanical strengthand cut/shear-resistance.

Aliphatic polyurethanes also can be prepared in accordance with thisinvention and these materials are preferably formed by reacting analiphatic diisocyanate with a polyol. Suitable aliphatic diisocyanatesthat may be used in accordance with this invention include, for example,isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HDI),4,4′-dicyclohexylmethane diisocyanate (“H₁₂ MDI”),meta-tetramethylxylyene diisocyanate (TMXDI), trans-cyclohexanediisocyanate (CHDI), and homopolymers and copolymers and blends thereof.Particularly suitable multi-functional isocyanates include trimers ofHDI or H₁₂ MDI, oligomers, or other derivatives thereof. The resultingpolyurethane generally has good light and thermal stability.

Any polyol available to one of ordinary skill in the art is suitable foruse according to the invention. Exemplary polyols include, but are notlimited to, polyether polyols, hydroxy-terminated polybutadiene(including partially/fully hydrogenated derivatives), polyester polyols,polycaprolactone polyols, and polycarbonate polyols. In one preferredembodiment, the polyol includes polyether polyol. Examples include, butare not limited to, polytetramethylene ether glycol (PTMEG) which isparticularly preferred, polyethylene propylene glycol, polyoxypropyleneglycol, and mixtures thereof. The hydrocarbon chain can have saturatedor unsaturated bonds and substituted or unsubstituted aromatic andcyclic groups.

In another embodiment, polyester polyols are included in thepolyurethane material. Suitable polyester polyols include, but are notlimited to, polyethylene adipate glycol; polybutylene adipate glycol;polyethylene propylene adipate glycol; o-phthalate-1,6-hexanediol;poly(hexamethylene adipate) glycol; and mixtures thereof. Thehydrocarbon chain can have saturated or unsaturated bonds, orsubstituted or unsubstituted aromatic and cyclic groups. In stillanother embodiment, polycaprolactone polyols are included in thematerials of the invention. Suitable polycaprolactone polyols include,but are not limited to: 1,6-hexanediol-initiated polycaprolactone,diethylene glycol initiated polycaprolactone, trimethylol propaneinitiated polycaprolactone, neopentyl glycol initiated polycaprolactone,1,4-butanediol-initiated polycaprolactone, and mixtures thereof. Thehydrocarbon chain can have saturated or unsaturated bonds, orsubstituted or unsubstituted aromatic and cyclic groups. In yet anotherembodiment, polycarbonate polyols are included in the polyurethanematerial of the invention. Suitable polycarbonates include, but are notlimited to, polyphthalate carbonate and poly(hexamethylene carbonate)glycol. The hydrocarbon chain can have saturated or unsaturated bonds,or substituted or unsubstituted aromatic and cyclic groups. In oneembodiment, the molecular weight of the polyol is from about 200 toabout 4000.

There are two basic techniques that can be used to make thepolyurethanes: a) one-shot technique, and b) prepolymer technique. Inthe one-shot technique, the diisocyanate, polyol, andhydroxyl-terminated chain-extender (curing agent) are reacted in onestep. On the other hand, the prepolymer technique involves a firstreaction between the diisocyanate and polyol compounds to produce apolyurethane prepolymer, and a subsequent reaction between theprepolymer and hydroxyl-terminated chain-extender. As a result of thereaction between the isocyanate and polyol compounds, there will be someunreacted NCO groups in the polyurethane prepolymer. The prepolymershould have less than 14% unreacted NCO groups. Preferably, theprepolymer has no greater than 8.5% unreacted NCO groups, morepreferably from 2.5% to 8%, and most preferably from 5.0% to 8.0%unreacted NCO groups. As the weight percent of unreacted isocyanategroups increases, the hardness of the composition also generallyincreases.

Either the one-shot or prepolymer method may be employed to produce thepolyurethane compositions of the invention. In one embodiment, theone-shot method is used, wherein the isocyanate compound is added to areaction vessel and then a curative mixture comprising the polyol andcuring agent is added to the reaction vessel. The components are mixedtogether so that the molar ratio of isocyanate groups to hydroxyl groupsis preferably in the range of about 1.00:1.00 to about 1.10:1.00. In asecond embodiment, the prepolymer method is used. In general, theprepolymer technique is preferred because it provides better control ofthe chemical reaction. The prepolymer method provides a more homogeneousmixture resulting in a more consistent polymer composition. The one-shotmethod results in a mixture that is inhomogeneous (more random) andaffords the manufacturer less control over the molecular structure ofthe resultant composition.

The polyurethane compositions can be formed by chain-extending thepolyurethane prepolymer with a single chain-extender or blend ofchain-extenders as described further below. As discussed above, thepolyurethane prepolymer can be chain-extended by reacting it with asingle chain-extender or blend of chain-extenders. In general, theprepolymer can be reacted with hydroxyl-terminated curing agents,amine-terminated curing agents, and mixtures thereof. The curing agentsextend the chain length of the prepolymer and build-up its molecularweight. In general, thermoplastic polyurethane compositions aretypically formed by reacting the isocyanate blend and polyols at a 1:1stoichiometric ratio. Thermoset compositions, on the other hand, arecross-linked polymers and are typically produced from the reaction ofthe isocyanate blend and polyols at normally a 1.05:1 stoichiometricratio

A catalyst may be employed to promote the reaction between theisocyanate and polyol compounds for producing the prepolymer or betweenprepolymer and chain-extender during the chain-extending step.Preferably, the catalyst is added to the reactants before producing theprepolymer. Suitable catalysts include, but are not limited to, bismuthcatalyst; zinc octoate; stannous octoate; tin catalysts such asbis-butyltin dilaurate, bis-butyltin diacetate, stannous octoate; tin(II) chloride, tin (IV) chloride, bis-butyltin dimethoxide,dimethyl-bis[1-oxonedecyl)oxy]stannane, di-n-octyltin bis-isooctylmercaptoacetate; amine catalysts such as triethylenediamine,triethylamine, and tributylamine; organic acids such as oleic acid andacetic acid; delayed catalysts; and mixtures thereof. The catalyst ispreferably added in an amount sufficient to catalyze the reaction of thecomponents in the reactive mixture. In one embodiment, the catalyst ispresent in an amount from about 0.001 percent to about 1 percent, andpreferably 0.1 to 0.5 percent, by weight of the composition.

The hydroxyl chain-extending (curing) agents are preferably selectedfrom the group consisting of ethylene glycol; diethylene glycol;polyethylene glycol; propylene glycol; 2-methyl-1,3-propanediol;2-methyl-1,4-butanediol; monoethanolamine; diethanolamine;triethanolamine; monoisopropanolamine; diisopropanolamine; dipropyleneglycol; polypropylene glycol; 1,2-butanediol; 1,3-butanediol;1,4-butanediol; 2,3-butanediol; 2,3-dimethyl-2,3-butanediol;trimethylolpropane; cyclohexyldimethylol; triisopropanolamine;N,N,N′,N′-tetra-(2-hydroxypropyl)-ethylene diamine; diethylene glycolbis-(aminopropyl) ether; 1,5-pentanediol; 1,6-hexanediol;1,3-bis-(2-hydroxyethoxy) cyclohexane; 1,4-cyclohexyldimethylol;1,3-bis-[2-(2-hydroxyethoxy) ethoxy]cyclohexane; 2,2′-(1,4-phenylenedioxy)diethanol, 1,3-bis-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}cyclohexane; trimethylolpropane; polytetramethylene etherglycol (PTMEG), preferably having a molecular weight from about 250 toabout 3900; and mixtures thereof.

Suitable amine chain-extending (curing) agents that can be used inchain-extending the polyurethane prepolymer include, but are not limitedto, unsaturated diamines such as 4,4′-diamino-diphenylmethane (i.e.,4,4′-methylene-dianiline or “MDA”), m-phenylenediamine,p-phenylenediamine, 1,2- or 1,4-bis(sec-butylamino)benzene,3,5-diethyl-(2,4- or 2,6-) toluenediamine or “DETDA”,3,5-dimethylthio-(2,4- or 2,6-)toluenediamine, 3,5-diethylthio-(2,4- or2,6-)toluenediamine, 3,3′-dimethyl-4,4′-diamino-diphenylmethane,3,3′-diethyl-5,5′-dimethyl4,4′-diamino-diphenylmethane (i.e.,4,4′-methylene-bis(2-ethyl-6-methyl-benezeneamine)),3,3′-dichloro-4,4′-diamino-diphenylmethane (i.e.,4,4′-methylene-bis(2-chloroaniline) or “MOCA”),3,3′,5,5′-tetraethyl-4,4′-diamino-diphenylmethane (i.e.,4,4′-methylene-bis(2,6-diethylaniline),2,2′-dichloro-3,3′,5,5′-tetraethyl-4,4′-diamino-diphenylmethane (i.e.,4,4′-methylene-bis(3-chloro-2,6-diethyleneaniline) or “MCDEA”),3,3′-diethyl-5,5′-dichloro-4,4′-diamino-diphenylmethane, or “MDEA”),3,3′-dichloro-2,2′,6,6′-tetraethyl-4,4′-diamino-diphenylmethane,3,3′-dichloro-4,4′-diamino-diphenylmethane,4,4′-methylene-bis(2,3-dichloroaniline) (i.e.,2,2′,3,3′-tetrachloro-4,4′-diamino-diphenylmethane or “MDCA”); andmixtures thereof. One particularly suitable amine-terminatedchain-extending agent is Ethacure 300™ (dimethylthiotoluenediamine or amixture of 2,6-diamino-3,5-dimethylthiotoluene and2,4-diamino-3,5-dimethylthiotoluene.) The amine curing agents used aschain extenders normally have a cyclic structure and a low molecularweight (250 or less).

When the polyurethane prepolymer is reacted with hydroxyl-terminatedcuring agents during the chain-extending step, as described above, theresulting polyurethane composition contains urethane linkages. On theother hand, when the polyurethane prepolymer is reacted withamine-terminated curing agents during the chain-extending step, anyexcess isocyanate groups in the prepolymer will react with the aminegroups in the curing agent. The resulting polyurethane compositioncontains urethane and urea linkages and may be referred to as apolyurethane/urea hybrid. The concentration of urethane and urealinkages in the hybrid composition may vary. In general, the hybridcomposition may contain a mixture of about 10 to 90% urethane and about90 to 10% urea linkages.

More particularly, when the polyurethane prepolymer is reacted withhydroxyl-terminated curing agents during the chain-extending step, asdescribed above, the resulting composition is essentially a purepolyurethane composition containing urethane linkages having thefollowing general structure:

where x is the chain length, i.e., about 1 or greater, and R and R₁ arestraight chain or branched hydrocarbon chain having about 1 to about 20carbons.

However, when the polyurethane prepolymer is reacted with anamine-terminated curing agent during the chain-extending step, anyexcess isocyanate groups in the prepolymer will react with the aminegroups in the curing agent and create urea linkages having the followinggeneral structure:

where x is the chain length, i.e., about 1 or greater, and R and R₁ arestraight chain or branched hydrocarbon chain having about 1 to about 20carbons.

The polyurethane compositions used to form the cover layer may containother polymer materials including, for example: aliphatic or aromaticpolyurethanes, aliphatic or aromatic polyureas, aliphatic or aromaticpolyurethane/urea hybrids, olefin-based copolymer ionomer compositions,polyethylene, including, for example, low density polyethylene, linearlow density polyethylene, and high density polyethylene; polypropylene;rubber-toughened olefin polymers; acid copolymers, for example,poly(meth)acrylic acid, which do not become part of an ionomericcopolymer; plastomers; flexomers; styrene/butadiene/styrene blockcopolymers; styrene/ethylene-butylene/styrene block copolymers;dynamically vulcanized elastomers; copolymers of ethylene and vinylacetates; copolymers of ethylene and methyl acrylates; polyvinylchloride resins; polyamides, poly(amide-ester) elastomers, and graftcopolymers of ionomer and polyamide including, for example, Pebax®thermoplastic polyether block amides, available from Arkema Inc;cross-linked trans-polyisoprene and blends thereof; polyester-basedthermoplastic elastomers, such as Hytrel®, available from DuPont;polyurethane-based thermoplastic elastomers, such as Elastollan®,available from BASF; polycarbonate/polyester blends such as Xylex®,available from SABIC Innovative Plastics; maleic anhydride-graftedpolymers such as Fusabond®, available from DuPont; and mixtures of theforegoing materials.

In addition, the polyurethane compositions may contain fillers,additives, and other ingredients that do not detract from the propertiesof the final composition. These additional materials include, but arenot limited to, catalysts, wetting agents, coloring agents, opticalbrighteners, cross-linking agents, whitening agents such as titaniumdioxide and zinc oxide, ultraviolet (UV) light absorbers, hindered aminelight stabilizers, defoaming agents, processing aids, surfactants, andother conventional additives. Other suitable additives includeantioxidants, stabilizers, softening agents, plasticizers, includinginternal and external plasticizers, impact modifiers, foaming agents,density-adjusting fillers, reinforcing materials, compatibilizers, andthe like. Some examples of useful fillers include zinc oxide, zincsulfate, barium carbonate, barium sulfate, calcium oxide, calciumcarbonate, clay, tungsten, tungsten carbide, silica, and mixturesthereof. Rubber regrind (recycled core material) and polymeric, ceramic,metal, and glass microspheres also may be used. Generally, the additiveswill be present in the composition in an amount between about 1 andabout 70 weight percent based on total weight of the compositiondepending upon the desired properties.

Thermoplastic polyurea compositions are typically formed by reacting theisocyanate blend and polyamines at a 1:1 stoichiometric ratio. Thepolyurea prepolymer can be chain-extended by reacting it with a singlecuring agent or blend of curing agents. In general, the prepolymer canbe reacted with hydroxyl-terminated curing agents, amine-terminatedcuring agents, or mixtures thereof. The curing agents extend the chainlength of the prepolymer and build-up its molecular weight. Normally,the prepolymer and curing agent are mixed so the isocyanate groups andhydroxyl or amine groups are mixed at a 1.05:1.00 stoichiometric ratio.

A catalyst may be employed to promote the reaction between theisocyanate and polyamine compounds for producing the prepolymer orbetween prepolymer and curing agent during the chain-extending step.Preferably, the catalyst is added to the reactants before producing theprepolymer. Suitable catalysts include, but are not limited to, thoseidentified above in connection with promoting the reaction between theisocyanate and polyol compounds for producing the prepolymer or betweenprepolymer and chain-extender during the chain-extending step.

The hydroxyl chain-extending (curing) agents are preferably selectedfrom the same group identified above in connection with polyurethanecompositions.

Suitable amine chain-extending (curing) agents that can be used inchain-extending the polyurea prepolymer of this invention include, butare not limited to those identified above in connection withchain-extending the polyurethane prepolymer, as well as4,4′-bis(sec-butylamino)-diphenylmethane,N,N′-dialkylamino-diphenylmethane,trimethyleneglycol-di(p-aminobenzoate),polyethyleneglycol-di(p-aminobenzoate),polytetramethyleneglycol-di(p-aminobenzoate); saturated diamines such asethylene diamine, 1,3-propylene diamine, 2-methyl-pentamethylenediamine, hexamethylene diamine, 2,2,4- and 2,4,4-trimethyl-1,6-hexanediamine, imino-bis(propylamine), imido-bis(propylamine),methylimino-bis(propylamine) (i.e.,N-(3-aminopropyl)-N-methyl-1,3-propanediamine),1,4-bis(3-aminopropoxy)butane (i.e.,3,3′-[1,4-butanediylbis-(oxy)bis]-1-propanamine),diethyleneglycol-bis(propylamine) (i.e.,diethyleneglycol-di(aminopropyl)ether),4,7,10-trioxatridecane-1,13-diamine, 1-methyl-2,6-diamino-cyclohexane,1,4-diamino-cyclohexane, poly(oxyethylene-oxypropylene) diamines, 1,3-or 1,4-bis(methylamino)-cyclohexane, isophorone diamine, 1,2- or1,4-bis(sec-butylamino)-cyclohexane, N,N′-diisopropyl-isophoronediamine, 4,4′-diamino-dicyclohexylmethane,3,3′-dimethyl-4,4′-diamino-dicyclohexylmethane,3,3′-dichloro-4,4′-diamino-dicyclohexylmethane,N,N′-dialkylamino-dicyclohexylmethane, polyoxyethylene diamines,3,3′-diethyl-5,5′-dimethyl-4,4′-diamino-dicyclohexylmethane,polyoxypropylene diamines,3,3′-diethyl-5,5′-dichloro-4,4′-diamino-dicyclohexylmethane,polytetramethylene ether diamines,3,3′,5,5′-tetraethyl-4,4′-diamino-dicyclohexylmethane (i.e.,4,4′-methylene-bis(2,6-diethylaminocyclohexane)),3,3′-dichloro-4,4′-diamino-dicyclohexylmethane,2,2′-dichloro-3,3′,5,5′-tetraethyl-4,4′-diamino-dicyclohexylmethane,(ethylene oxide)-capped polyoxypropylene ether diamines,2,2′,3,3′-tetrachloro-4,4′-diamino-dicyclohexylmethane,4,4′-bis(sec-butylamino)-dicyclohexylmethane; triamines such asdiethylene triamine, dipropylene triamine, (propylene oxide)-basedtriamines (i.e., polyoxypropylene triamines),N-(2-aminoethyl)-1,3-propylenediamine (i.e., N₃-amine), glycerin-basedtriamines, (all saturated); tetramines such asN,N′-bis(3-aminopropyl)ethylene diamine (i.e., N₄-amine) (bothsaturated), triethylene tetramine; and other polyamines such astetraethylene pentamine (also saturated).

When the polyurea prepolymer is reacted with amine-terminated curingagents during the chain-extending step, as described above, theresulting composition is essentially a pure polyurea composition.

On the other hand, when the polyurea prepolymer is reacted with ahydroxyl-terminated curing agent during the chain-extending step, anyexcess isocyanate groups in the prepolymer will react with the hydroxylgroups in the curing agent and create urethane linkages to form apolyurea-urethane hybrid. Herein, the terms urea and polyurea are usedinterchangeably.

This chain-extending step, which occurs when the polyurea prepolymer isreacted with hydroxyl curing agents, amine curing agents, or mixturesthereof, builds-up the molecular weight and extends the chain length ofthe prepolymer. When the polyurea prepolymer is reacted with aminecuring agents, a polyurea composition having urea linkages is produced.

When the polyurea prepolymer is reacted with hydroxyl curing agents, apolyurea/urethane hybrid composition containing both urea and urethanelinkages is produced. The polyurea/urethane hybrid composition isdistinct from the pure polyurea composition. The concentration of ureaand urethane linkages in the hybrid composition may vary. In general,the hybrid composition may contain a mixture of about 10 to 90% urea andabout 90 to 10% urethane linkages. The resulting polyurea orpolyurea/urethane hybrid composition has elastomeric properties based onphase separation of the soft and hard segments. The soft segments, whichare formed from the polyamine reactants, are generally flexible andmobile, while the hard segments, which are formed from the isocyanatesand chain extenders, are generally stiff and immobile.

Additional suitable materials for golf ball layers include but are notlimited to ionomers (e.g. Surlyn®, HNPs, etc.) and blends thereof. Theionomer may include, for example, partially-neutralized ionomers andhighly-neutralized ionomers (HNPs), including ionomers formed fromblends of two or more partially-neutralized ionomers, blends of two ormore highly-neutralized ionomers, and blends of one or morepartially-neutralized ionomers with one or more highly-neutralizedionomers.

Ionomers, are typically ethylene/acrylic acid copolymers orethylene/acrylic acid/acrylate terpolymers in which some or all of theacid groups are neutralized with metal cations such as na, li, mg,and/or zn. Non-limiting examples of commercially available ionomerssuitable for use with the present invention include for example SURLYNs®from DuPont and Ioteks® from Exxon. SURLYN® 8940 (Na), SURLYN® 9650(Zn), and SURLYN® 9910 (Zn) are examples of low acid ionomer resins withthe acid groups that have been neutralized to a certain degree with acation. More examples of suitable low acid ionomers, e.g., Escor®4000/7030 and Escor® 900/8000, are disclosed in U.S. Pat. Nos. 4,911,451and 4,884,814, the disclosures of which are incorporated by referenceherein. High acid ionomer resins include SURLYN(® 8140 (Na) and SURLYN®8546 (Li), which have an methacrylic acid content of about 19 percent.The acid groups of these high acid ionomer resins that have beenneutralized to a certain degree with the designated cation.

Ionomers may encompass those polymers obtained by copolymerization of anacidic or basic monomer, such as alkyl (meth)acrylate, with at least oneother comonomer, such as an olefin, styrene or vinyl acetate, followedby at least partial neutralization.

Alternatively, acidic or basic groups may be incorporated into a polymerto form an ionomer by reacting the polymer, such as polystyrene or apolystyrene copolymer including a block copolymer of polystyrene, with afunctionality reagent, such as a carboxylic acid or sulfonic acid,followed by at least partial neutralization. Suitable neutralizingsources include cations for negatively charged acidic groups and anionsfor positively charged basic groups.

For example, ionomers may be obtained by providing a cross metallic bondto polymers of monoolefin with at least one member selected from thegroup consisting of unsaturated mono- or di-carboxylic acids having 3 to12 carbon atoms and esters thereof (the polymer contains about 1 percentto about 50 percent by weight of the unsaturated mono- or di-carboxylicacid and/or ester thereof). In one embodiment, the ionomer is an E/X/Ycopolymers where E is ethylene, X is a softening comonomer, such asacrylate or methacrylate, present in 0 percent to about 50 percent byweight of the polymer (preferably 0 weight percent to about 25 weightpercent, most preferably 0 weight percent to about 20 weight percent),and Y is acrylic or methacrylic acid present in about 5 to about 35weight percent of the polymer, wherein the acid moiety is neutralizedabout 1 percent to about 100 percent (preferably at least about 40percent, most preferably at least about 60 percent) to form an ionomerby a cation such as lithium, sodium, potassium, magnesium, calcium,barium, lead, tin, zinc, or aluminum, or a combination of such cations.

Any of the acid-containing ethylene copolymers discussed above may beused to form an ionomer according to the present invention. In addition,the ionomer may be a low acid or high acid ionomer. As detailed above, ahigh acid ionomer may be a copolymer of an olefin, e.g., ethylene, andat least 16 weight percent of an α,β-ethylenically unsaturatedcarboxylic acid, e.g., acrylic or methacrylic acid, wherein about 10percent to about 100 percent of the carboxylic acid groups areneutralized with a metal ion. In contrast, a low acid ionomer containsabout 15 weight percent of the α,β-ethylenically unsaturated carboxylicacid.

Suitable commercially available ionomer resins include SURLYNs® (DuPont)and Ioteks® (Exxon). Other suitable ionomers for use in the blends ofthe present invention include polyolefins, polyesters, polystyrenes,SBS, SEBS, and polyurethanes, in the form of homopolymers, copolymers,or block copolymer ionomers.

The ionomers may also be blended with highly neutralized polymers (HNP).As used herein, a highly neutralized polymer has greater than about 70percent of the acid groups neutralized. In one embodiment, about 80percent or greater of the acid groups are neutralized. In anotherembodiment, about 90 percent or greater of the acid groups areneutralized. In still another embodiment, the HNP is a fully neutralizedpolymers, i.e., all of the acid groups (100 percent) in the polymercomposition are neutralized.

Suitable HNPs include, but are not limited to, polymers containingα,β-unsaturated carboxylic acid groups, or the salts thereof, that havebeen highly neutralized by organic fatty acids. Such HNPs arecommercially available from DuPont under the trade name HPF, e.g., HPF1000 and HPF 2000. The HNP can also be formed using an oxa-containingcompound as a reactive processing aid to avoid processing problems, asdisclosed in U.S. Patent Publication No. 2003/0225197. In particular, anHNP can include a thermoplastic resin component having an acid or ionicgroup, i.e., an acid polymer or partially neutralized polymer, combinedwith an oxa acid, an oxa salt, an oxa ester, or combination thereof andan inorganic metal compound or organic amine compound.

As used herein, a partially neutralized polymer should be understood tomean polymers with about 10 to about 70 percent of the acid groupsneutralized. For example, the HNP can includes about 10 percent to about30 percent by weight of at least one oxa acid, about 70 percent to about90 percent by weight of at least one thermoplastic resin component, andabout 2 percent to about 6 percent by weight of an inorganic metalcompound, organic amine, or a combination thereof.

In addition, the HNP can be formed from an acid copolymer that isneutralized by one or more amine-based or ammonium-based components, ormixtures thereof, as disclosed in co-pending U.S. patent applicationSer. No. 10/875,725, filed Jun. 25, 2004, entitled “Golf BallCompositions Neutralized with Ammonium-Based and Amine-Based Compounds,”which is incorporated in its entirety by reference herein.

Furthermore, those of ordinary skill in the art will appreciate that theHNPs may be neutralized using one or more of the above methods. Forexample, an acid copolymer that is partially or highly neutralized in amanner described above may be subjected to additional neutralizationusing more traditional processes, e.g., neutralization with salts oforganic fatty acids and/or a suitable cation source.

In a particular embodiment, the core includes at least one additionalthermoplastic intermediate core layer formed from a compositioncomprising an ionomer selected from DuPont HPF ESX 367, HPF 1000, HPF2000, HPF AD1035, HPF AD1035 Soft, HPF AD1040, and AD1172 ionomers,commercially available from E. I. du Pont de Nemours and Company.

The coefficient of restitution (“COR”), compression, and surfacehardness of each of these materials, as measured on 1.55″ injectionmolded spheres aged two weeks at 23° C./50% RH, are given in Table 2below.

TABLE 2 Solid Sphere Solid Sphere Solid Sphere Shore D Example CORCompression Surface Hardness HPF 1000 0.830 115 54 HPF 2000 0.860 90 47HPF AD1035 0.820 63 42 HPF AD 1035 Soft 0.780 33 35 HPF AD 1040 0.855135 60 HPF AD1172 0.800 32 37

In one embodiment, an intermediate layer is disposed between the singleor multi-layered core and surrounding cover layer. These intermediatelayers also can be referred to as casing or inner cover layers. Theintermediate layer can be formed from any materials known in the art,including thermoplastic and thermosetting materials, but preferably isformed of an ionomer composition comprising an ethylene acid copolymercontaining acid groups that are at least partially neutralized. Suitableethylene acid copolymers that may be used to form the intermediatelayers are generally referred to as copolymers of ethylene; C₃ to C₈α,β-ethylenically unsaturated mono- or dicarboxylic acid; and optionalsoftening monomer. These ethylene acid copolymer ionomers also can beused to form the inner core and outer core layers as described above.

Suitable ionomer compositions include partially-neutralized ionomers andhighly-neutralized ionomers (HNPs), including ionomers formed fromblends of two or more partially-neutralized ionomers, blends of two ormore highly-neutralized ionomers, and blends of one or morepartially-neutralized ionomers with one or more highly-neutralizedionomers. For purposes of the present disclosure, “HNP” refers to anacid copolymer after at least 70% of all acid groups present in thecomposition are neutralized. Preferred ionomers are salts of O/X- andO/X/Y-type acid copolymers, wherein O is an α-olefin, X is a C₃-C₈α,β-ethylenically unsaturated carboxylic acid, and Y is a softeningmonomer. O is preferably selected from ethylene and propylene. X ispreferably selected from methacrylic acid, acrylic acid, ethacrylicacid, crotonic acid, and itaconic acid. Methacrylic acid and acrylicacid are particularly preferred. Y is preferably selected from (meth)acrylate and alkyl (meth) acrylates wherein the alkyl groups have from 1to 8 carbon atoms, including, but not limited to, n-butyl (meth)acrylate, isobutyl (meth) acrylate, methyl (meth) acrylate, and ethyl(meth) acrylate.

Preferred O/X and O/X/Y-type copolymers include, without limitation,ethylene acid copolymers, such as ethylene/(meth)acrylic acid,ethylene/(meth)acrylic acid/maleic anhydride, ethylene/(meth)acrylicacid/maleic acid mono-ester, ethylene/maleic acid, ethylene/maleic acidmono-ester, ethylene/(meth)acrylic acid/n-butyl (meth)acrylate,ethylene/(meth)acrylic acid/iso-butyl (meth)acrylate,ethylene/(meth)acrylic acid/methyl (meth)acrylate,ethylene/(meth)acrylic acid/ethyl (meth)acrylate terpolymers, and thelike. The term, “copolymer,” as used herein, includes polymers havingtwo types of monomers, those having three types of monomers, and thosehaving more than three types of monomers. Preferred α,β-ethylenicallyunsaturated mono- or dicarboxylic acids are (meth) acrylic acid,ethacrylic acid, maleic acid, crotonic acid, fumaric acid, itaconicacid. (Meth) acrylic acid is most preferred. As used herein, “(meth)acrylic acid” means methacrylic acid and/or acrylic acid. Likewise,“(meth) acrylate” means methacrylate and/or acrylate.

In a particularly preferred version, highly neutralized E/X- andE/X/Y-type acid copolymers, wherein E is ethylene, X is a C₃-C₈α,β-ethylenically unsaturated carboxylic acid, and Y is a softeningmonomer are used. X is preferably selected from methacrylic acid,acrylic acid, ethacrylic acid, crotonic acid, and itaconic acid.Methacrylic acid and acrylic acid are particularly preferred. Y ispreferably an acrylate selected from alkyl acrylates and aryl acrylatesand preferably selected from (meth) acrylate and alkyl (meth) acrylateswherein the alkyl groups have from 1 to 8 carbon atoms, including, butnot limited to, n-butyl (meth) acrylate, isobutyl (meth) acrylate,methyl (meth) acrylate, and ethyl (meth) acrylate. Preferred E/X/Y-typecopolymers are those wherein X is (meth) acrylic acid and/or Y isselected from (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth)acrylate, methyl (meth) acrylate, and ethyl (meth) acrylate. Morepreferred E/X/Y-type copolymers are ethylene/(meth) acrylic acid/n-butylacrylate, ethylene/(meth) acrylic acid/methyl acrylate, andethylene/(meth) acrylic acid/ethyl acrylate.

The amount of ethylene in the acid copolymer is typically at least 15wt. %, preferably at least 25 wt. %, more preferably least 40 wt. %, andeven more preferably at least 60 wt. %, based on total weight of thecopolymer. The amount of C₃ to C₈ α,β-ethylenically unsaturated mono- ordicarboxylic acid in the acid copolymer is typically from 1 wt. % to 35wt. %, preferably from 5 wt. % to 30 wt. %, more preferably from 5 wt. %to 25 wt. %, and even more preferably from 10 wt. % to 20 wt. %, basedon total weight of the copolymer. The amount of optional softeningcomonomer in the acid copolymer is typically from 0 wt. % to 50 wt. %,preferably from 5 wt. % to 40 wt. %, more preferably from 10 wt. % to 35wt. %, and even more preferably from 20 wt. % to 30 wt. %, based ontotal weight of the copolymer. “Low acid” and “high acid” ionomericpolymers, as well as blends of such ionomers, may be used. In general,low acid ionomers are considered to be those containing 16 wt. % or lessof acid moieties, whereas high acid ionomers are considered to be thosecontaining greater than 16 wt. % of acid moieties.

The various O/X, E/X, O/X/Y, and E/X/Y-type copolymers are at leastpartially neutralized with a cation source, optionally in the presenceof a high molecular weight organic acid, such as those disclosed in U.S.Pat. No. 6,756,436, the entire disclosure of which is herebyincorporated herein by reference. The acid copolymer can be reacted withthe optional high molecular weight organic acid and the cation sourcesimultaneously, or prior to the addition of the cation source. Suitablecation sources include, but are not limited to, metal ion sources, suchas compounds of alkali metals, alkaline earth metals, transition metals,and rare earth elements; ammonium salts and monoamine salts; andcombinations thereof. Preferred cation sources are compounds ofmagnesium, sodium, potassium, cesium, calcium, barium, manganese,copper, zinc, lead, tin, aluminum, nickel, chromium, lithium, and rareearth metals.

Other suitable thermoplastic polymers that may be used to form theadjacent casing, intermediate and/or inner cover layer, but are notlimited to, the following polymers (including homopolymers, copolymers,and derivatives thereof: (a) polyester, particularly those modified witha compatibilizing group such as sulfonate or phosphonate, includingmodified poly(ethylene terephthalate), modified poly(butyleneterephthalate), modified poly(propylene terephthalate), modifiedpoly(trimethylene terephthalate), modified poly(ethylene naphthenate),and those disclosed in U.S. Pat. Nos. 6,353,050, 6,274,298, and6,001,930, the entire disclosures of which are hereby incorporatedherein by reference, and blends of two or more thereof; (b) polyamides,polyamide-ethers, and polyamide-esters, and those disclosed in U.S. Pat.Nos. 6,187,864, 6,001,930, and 5,981,654, the entire disclosures ofwhich are hereby incorporated herein by reference, and blends of two ormore thereof (c) polyurethanes, polyureas, polyurethane-polyureahybrids, and blends of two or more thereof; (d) fluoropolymers, such asthose disclosed in U.S. Pat. Nos. 5,691,066, 6,747,110 and 7,009,002,the entire disclosures of which are hereby incorporated herein byreference, and blends of two or more therof; (e) polystyrenes, such aspoly(styrene-co-maleic anhydride), acrylonitrile-butadiene-styrene,poly(styrene sulfonate), polyethylene styrene, and blends of two or morethereof; (f) polyvinyl chlorides and grafted polyvinyl chlorides, andblends of two or more thereof; (g) polycarbonates, blends ofpolycarbonate/acrylonitrile-butadiene-styrene, blends ofpolycarbonate/polyurethane, blends of polycarbonate/polyester, andblends of two or more thereof; (h) polyethers, such as polyaryleneethers, polyphenylene oxides, block copolymers of alkenyl aromatics withvinyl aromatics and polyamicesters, and blends of two or more thereof;(i) polyimides, polyetherketones, polyamideimides, and blends of two ormore thereof; and (j) polycarbonate/polyester copolymers and blends.

Those layers of golf balls of the invention comprising conventionalthermoplastic or thermoset materials may be formed using a variety ofconventional application techniques such as compression molding, flipmolding, injection molding, retractable pin injection molding, reactioninjection molding (RIM), liquid injection molding (LIM), casting, vacuumforming, powder coating, flow coating, spin coating, dipping, spraying,and the like. Conventionally, compression molding and injection moldingare applied to thermoplastic materials, whereas RIM, liquid injectionmolding, and casting are employed on thermoset materials. These andother manufacture methods are disclosed in U.S. Pat. Nos. 6,207,784 and5,484,870, the disclosures of which are incorporated herein by referencein their entireties.

A method of injection molding using a split vent pin can be found inco-pending U.S. Pat. No. 6,877,974, filed Dec. 22, 2000, entitled “SplitVent Pin for Injection Molding.” Examples of retractable pin injectionmolding may be found in U.S. Pat. Nos. 6,129,881; 6,235,230; and6,379,138. These molding references are incorporated in their entiretyby reference herein. In addition, a chilled chamber, i.e., a coolingjacket, such as the one disclosed in U.S. Pat. No. 6,936,205, filed Nov.22, 2000, entitled “Method of Making Golf Balls” may be used to cool thecompositions of the invention when casting, which also allows for ahigher loading of catalyst into the system.

Golf balls of the invention include at least one compression moldedlayer comprising or consisting of any extrudate that can be preformedaccording to methods of the invention—including, for example, extrudatescomprised of rubber-based compositions. Conventionally, compressionmolding and injection molding are applied to thermoplastic materials,whereas RIM, liquid injection molding, and casting are employed onthermoset materials. These and other manufacture methods are disclosedin U.S. Pat. Nos. 5,484,870; 5,935,500; 6,207,784; 6,436,327; 7,648,667;6,562,912; 6,913,726; 7,204,946; 8,980,151; 9,211,662; U.S. Publs. Nos.2003/0067088; and 2013/0072323; the disclosures of each of which areincorporated herein by reference in their entirety.

Castable reactive liquid polyurethanes and polyurea materials may beapplied over the inner ball using a variety of application techniquessuch as casting, injection molding spraying, compression molding,dipping, spin coating, or flow coating methods that are well known inthe art. In one embodiment, the castable reactive polyurethanes andpolyurea material is formed over the core using a combination of castingand compression molding. Conventionally, compression molding andinjection molding are applied to thermoplastic cover materials, whereasRIM, liquid injection molding, and casting are employed on thermosetcover materials.

U.S. Pat. No. 5,733,428, the entire disclosure of which is herebyincorporated by reference, discloses a method for forming a polyurethanecover on a golf ball core. Because this method relates to the use ofboth casting thermosetting and thermoplastic material as the golf ballcover, wherein the cover is formed around the core by mixing andintroducing the material in mold halves, the polyurea compositions mayalso be used employing the same casting process.

For example, once a polyurea composition is mixed, an exothermicreaction commences and continues until the material is solidified aroundthe core. It is important that the viscosity be measured over time, sothat the subsequent steps of filling each mold half, introducing thecore into one half and closing the mold can be properly timed foraccomplishing centering of the core cover halves fusion and achievingoverall uniformity. A suitable viscosity range of the curing urea mixfor introducing cores into the mold halves is determined to beapproximately between about 2,000 cP and about 30,000 cP, or within arange of about 8,000 cP to about 15,000 cP.

To start the cover formation, mixing of the prepolymer and curative isaccomplished in a motorized mixer inside a mixing head by feedingthrough lines metered amounts of curative and prepolymer. Top preheatedmold halves are filled and placed in fixture units using centering pinsmoving into apertures in each mold. At a later time, the cavity of abottom mold half, or the cavities of a series of bottom mold halves, isfilled with similar mixture amounts as used for the top mold halves.After the reacting materials have resided in top mold halves for about40 to about 100 seconds, preferably for about 70 to about 80 seconds, acore is lowered at a controlled speed into the gelling reacting mixture.

A ball cup holds the shell through reduced pressure (or partial vacuum).Upon location of the core in the halves of the mold after gelling forabout 4 to about 12 seconds, the vacuum is released allowing the core tobe released. In one embodiment, the vacuum is released allowing the coreto be released after about 5 seconds to 10 seconds. The mold halves,with core and solidified cover half thereon, are removed from thecentering fixture unit, inverted and mated with second mold halveswhich, at an appropriate time earlier, have had a selected quantity ofreacting polyurea prepolymer and curing agent introduced therein tocommence gelling.

Similarly, U.S. Pat. Nos. 5,006,297 and 5,334,673 both also disclosesuitable molding techniques that may be utilized to apply the castablereactive liquids employed in the present invention.

However, golf balls of the invention may be made by any known techniqueto those skilled in the art.

Examples of yet other materials which may be suitable for incorporatingand coordinating in order to target and achieve desired playingcharacteristics or feel include plasticized thermoplastics,polyalkenamer compositions, polyester-based thermoplastic elastomerscontaining plasticizers, transparent or plasticized polyamides, thiolenecompositions, poly-amide and anhydride-modified polyolefins, organicacid-modified polymers, and the like.

The solid cores for the golf balls of this invention may be made usingany suitable conventional technique such as, for example, compression orinjection-molding, Typically, the cores are formed by compressionmolding a slug of uncured or lightly cured rubber material into aspherical structure. Prior to forming the cover layer, the corestructure may be surface-treated to increase the adhesion between itsouter surface and adjacent layer. Such surface-treatment may includemechanically or chemically-abrading the outer surface of the core. Forexample, the core may be subjected to corona-discharge,plasma-treatment, silane-dipping, or other treatment methods known tothose in the art. The cover layers are formed over the core or ballsub-assembly (the core structure and any intermediate layers disposedabout the core) using any suitable method as described further below.Prior to forming the cover layers, the ball sub-assembly may besurface-treated to increase the adhesion between its outer surface andthe overlying cover material using the above-described techniques.

Conventional compression and injection-molding and other methods can beused to form cover layers over the core or ball sub-assembly. Ingeneral, compression molding normally involves first making half(hemispherical) shells by injection-molding the composition in aninjection mold or creating preforms from exturdate. This producessemi-cured, semi-rigid half-shells (or cups). Then, the half-shells arepositioned in a compression mold around the core or ball sub-assembly.Heat and pressure are applied and the half-shells fuse together to forma cover layer over the core or sub-assembly. Compression molding alsocan be used to cure the cover composition after injection-molding. Forexample, a thermally-curable composition can be injection-molded arounda core in an unheated mold. After the composition is partially hardened,the ball is removed and placed in a compression mold. Heat and pressureare applied to the ball and this causes thermal-curing of the outercover layer.

Retractable pin injection-molding (RPIM) methods generally involve usingupper and lower mold cavities that are mated together. The upper andlower mold cavities form a spherical interior cavity when they arejoined together. The mold cavities used to form the outer cover layerhave interior dimple cavity details. The cover material conforms to theinterior geometry of the mold cavities to form a dimple pattern on thesurface of the ball. The injection-mold includes retractable supportpins positioned throughout the mold cavities. The retractable supportpins move in and out of the cavity. The support pins help maintain theposition of the core or ball sub-assembly while the molten compositionflows through the mold gates. The molten composition flows into thecavity between the core and mold cavities to surround the core and formthe cover layer. Other methods can be used to make the cover including,for example, reaction injection-molding (RIM), liquid injection-molding,casting, spraying, powder-coating, vacuum-forming, flow-coating,dipping, spin-coating, and the like.

As discussed above, an inner cover layer or intermediate layer,preferably formed from an ethylene acid copolymer ionomer composition,can be formed between the core or ball sub-assembly and cover layer. Theintermediate layer comprising the ionomer composition may be formedusing a conventional technique such as, for example, compression orinjection-molding. For example, the ionomer composition may beinjection-molded or placed in a compression mold to produce half-shells.These shells are placed around the core in a compression mold, and theshells fuse together to form an intermediate layer. Alternatively, theionomer composition is injection-molded directly onto the core usingretractable pin injection-molding.

After the golf balls have been removed from the mold, they may besubjected to finishing steps such as flash-trimming, surface-treatment,marking, and one or more coating layer may be applied as desired viamethods such as spraying, dipping, brushing, or rolling. Then the golfball can go through a series of finishing steps.

For example, in traditional white-colored golf balls, thewhite-pigmented outer cover layer may be surface-treated using asuitable method such as, for example, corona, plasma, or ultraviolet(UV) light-treatment. In another finishing process, the golf balls arepainted with one or more paint coatings. For example, white or clearprimer paint may be applied first to the surface of the ball and thenindicia may be applied over the primer followed by application of aclear polyurethane top-coat. Indicia such as trademarks, symbols, logos,letters, and the like may be printed on the outer cover or prime-coatedlayer, or top-coated layer using pad-printing, ink-jet printing,dye-sublimation, or other suitable printing methods. Any of the surfacecoatings may contain a fluorescent optical brightener.

Golf balls of the invention may also include at least one intermediatelayer. Herein, the term “intermediate layer” includes any layer disposedbetween the outermost core layer and the outermost cover layer such asmantle layers, inner cover layers, moisture barrier layers, coatings,film layers, casing layers, and the like. Intermediate layers maylikewise also comprise materials generally used in cores and covers asdescribed herein for example.

In one non-limiting embodiment, an intermediate layer having a thicknessof about 0.010 inches to about 0.06 inches, is disposed about a corehaving a diameter ranging from about 1.5 inches to about 1.59 inches.

Intermediate layer(s) may be formed, at least in part, from one or morehomopolymeric or copolymeric materials, such as ionomers, primarily orfully non-ionomeric thermoplastic materials, vinyl resins, polyolefins,polyurethanes, polyureas, polyamides, acrylic resins and blends thereof,olefinic thermoplastic rubbers, block copolymers of styrene andbutadiene, isoprene or ethylene-butylene rubber, copoly(ether-amide),polyphenylene oxide resins or blends thereof, and thermoplasticpolyesters. However, embodiments are envisioned wherein at least oneintermediate layer is formed from a different material commonly used ina core and/or cover layer.

The range of thicknesses for an intermediate layer of a golf ball islarge because of the vast possibilities when using an intermediatelayer, i.e., as an outer core layer, an inner cover layer, a woundlayer, a moisture/vapor barrier layer. When used in a golf ball of thepresent invention, the intermediate layer, or inner cover layer, mayhave a thickness about 0.3 inches or less. In one embodiment, thethickness of the intermediate layer is from about 0.002 inches to about0.1 inches, and preferably about 0.01 inches or greater.

For example, the intermediate layer and/or inner cover layer may have athickness ranging from about 0.010 inches to about 0.06 inches. Inanother embodiment, the intermediate layer thickness is about 0.05inches or less, or about 0.01 inches to about 0.045 inches for example.

If the ball includes an intermediate layer or inner cover layer, thehardness (material) may for example be about 50 Shore D or greater, morepreferably about 55 Shore D or greater, and most preferably about 60Shore D or greater. In one embodiment, the inner cover has a Shore Dhardness of about 62 to about 90 Shore D. In one example, the innercover has a hardness of about 68 Shore D or greater. In addition, thethickness of the inner cover layer is preferably about 0.015 inches toabout 0.100 inches, more preferably about 0.020 inches to about 0.080inches, and most preferably about 0.030 inches to about 0.050 inches,but once again, may be changed to target playing characteristics.

The cover typically has a thickness to provide sufficient strength, goodperformance characteristics, and durability. In one embodiment, thecover thickness may for example be from about 0.02 inches to about 0.12inches, or about 0.1 inches or less. For example, the cover may be partof a two-piece golf ball and have a thickness ranging from about 0.03inches to about 0.09 inches. In another embodiment, the cover thicknessmay be about 0.05 inches or less, or from about 0.02 inches to about0.05 inches, or from about 0.02 inches and about 0.045 inches.

The cover may be a single-, dual-, or multi-layer cover and have anoverall thickness for example within a range having a lower limit of0.010 or 0.020 or 0.025 or 0.030 or 0.040 or 0.045 inches and an upperlimit of 0.050 or 0.060 or 0.070 or 0.075 or 0.080 or 0.090 or 0.100 or0.150 or 0.200 or 0.300 or 0.500 inches. In a particular embodiment, thecover may be a single layer having a thickness of from 0.010 or 0.020 or0.025 inches to 0.035 or 0.040 or 0.050 inches. In another particularembodiment, the cover may consist of an inner cover layer having athickness of from 0.010 or 0.020 or 0.025 inches to 0.035 or 0.050inches and an outer cover layer having a thickness of from 0.010 or0.020 or 0.025 inches to 0.035 or 0.040 inches.

The outer cover preferably has a thickness within a range having a lowerlimit of about 0.004 or 0.010 or 0.020 or 0.030 or 0.040 inches and anupper limit of about 0.050 or 0.055 or 0.065 or 0.070 or 0.080 inches.Preferably, the thickness of the outer cover is about 0.020 inches orless. The outer cover preferably has a surface hardness of 75 Shore D orless, 65 Shore D or less, or 55 Shore D or less, or 50 Shore D or less,or 50 Shore D or less, or 45 Shore D or less. Preferably, the outercover has hardness in the range of about 20 to about 70 Shore D. In oneexample, the outer cover has hardness in the range of about 25 to about65 Shore D.

In one embodiment, the cover may be a single layer having a surfacehardness for example of 60 Shore D or greater, or 65 Shore D or greater.In a particular aspect of this embodiment, the cover is formed from acomposition having a material hardness of 60 Shore D or greater, or 65Shore D or greater.

In another particular embodiment, the cover may be a single layer havinga thickness of from 0.010 or 0.020 inches to 0.035 or 0.050 inches andformed from a composition having a material hardness of from 60 or 62 or65 Shore D to 65 or 70 or 72 Shore D.

In yet another particular embodiment, the cover is a single layer havinga thickness of from 0.010 or 0.025 inches to 0.035 or 0.040 inches andformed from a composition having a material hardness of 62 Shore D orless, or less than 62 Shore D, or 60 Shore D or less, or less than 60Shore D, or 55 Shore D or less, or less than 55 Shore D.

In still another particular embodiment, the cover is a single layerhaving a thickness of from 0.010 or 0.025 inches to 0.035 or 0.040inches and formed from a composition having a material hardness of 62Shore D or less, or less than 62 Shore D, or 60 Shore D or less, or lessthan 60 Shore D, or 55 Shore D or less, or less than 55 Shore D.

In an alternative embodiment, the cover may comprise an inner coverlayer and an outer cover layer. The inner cover layer composition mayhave a material hardness of from 60 or 62 or 65 Shore D to 65 or 70 or72 Shore D. The inner cover layer may have a thickness within a rangehaving a lower limit of 0.010 or 0.020 or 0.030 inches and an upperlimit of 0.035 or 0.040 or 0.050 inches. The outer cover layercomposition may have a material hardness of 62 Shore D or less, or lessthan 62 Shore D, or 60 Shore D or less, or less than 60 Shore D, or 55Shore D or less, or less than 55 Shore D. The outer cover layer may havea thickness within a range having a lower limit of 0.010 or 0.020 or0.025 inches and an upper limit of 0.035 or 0.040 or 0.050 inches.

In yet another embodiment, the cover is a dual- or multi-layer coverincluding an inner or intermediate cover layer and an outer cover layer.The inner cover layer may have a surface hardness of 70 Shore D or less,or 65 Shore D or less, or less than 65 Shore D, or a Shore D hardness offrom 50 to 65, or a Shore D hardness of from 57 to 60, or a Shore Dhardness of 58, and a thickness within a range having a lower limit of0.010 or 0.020 or 0.030 inches and an upper limit of 0.045 or 0.080 or0.120 inches. The outer cover layer may have a material hardness of 65Shore D or less, or 55 Shore D or less, or 45 Shore D or less, or 40Shore D or less, or from 25 Shore D to 40 Shore D, or from 30 Shore D to40 Shore D. The outer cover layer may have a surface hardness within arange having a lower limit of 20 or 30 or 35 or 40 Shore D and an upperlimit of 52 or 58 or 60 or 65 or 70 or 72 or 75 Shore D. The outer coverlayer may have a thickness within a range having a lower limit of 0.010or 0.015 or 0.025 inches and an upper limit of 0.035 or 0.040 or 0.045or 0.050 or 0.055 or 0.075 or 0.080 or 0.115 inches.

All this being said, embodiments are also envisioned wherein one or moreof the cover layers is formed from a material typically incorporated ina core or intermediate layer.

It is envisioned that golf balls of the invention may also incorporateconventional coating layer(s) for the purposes usually incorporated. Forexample, one or more coating layer may have a combined thickness of fromabout 0.1 μm to about 100 μm, or from about 2 μm to about 50 μm, or fromabout 2 μm to about 30 μm. Meanwhile, each coating layer may have athickness of from about 0.1 μm to about 50 μm, or from about 0.1 μm toabout 25 μm, or from about 0.1 μm to about 14 μm, or from about 2 μm toabout 9 μm, for example.

It is envisioned that layers a golf ball of the invention other than theinventive compression molded layer may be incorporated via any ofcasting, compression molding, injection molding, or thermoforming asdesired.

The resulting balls of this invention have good impact durability andcut/shear-resistance. The United States Golf Association (“USGA”) hasset total weight limits for golf balls. Particularly, the USGA hasestablished a maximum weight of 45.93 g (1.62 ounces) for golf balls.There is no lower weight limit. In addition, the USGA requires that golfballs used in competition have a diameter of at least 1.68 inches. Thereis no upper limit so many golf balls have an overall diameter fallingwithin the range of about 1.68 to about 1.80 inches. The golf balldiameter is preferably about 1.68 to 1.74 inches, more preferably about1.68 to 1.70 inches. In accordance with the present invention, theweight, diameter, and thickness of the core and cover layers may beadjusted, as needed, so the ball meets USGA specifications of a maximumweight of 1.62 ounces and a minimum diameter of at least 1.68 inches.

Preferably, the golf ball has a Coefficient of Restitution (CoR) of atleast 0.750 and more preferably at least 0.800 (as measured per the testmethods below). The core of the golf ball generally has a compression inthe range of about 30 to about 130 and more preferably in the range ofabout 70 to about 110 (as measured per the test methods below.) Theseproperties allow players to generate greater ball velocity off the teeand achieve greater distance with their drives. At the same time, therelatively thin outer cover layer means that a player will have a morecomfortable and natural feeling when striking the ball with a club. Theball is more playable and its flight path can be controlled more easily.This control allows the player to make better approach shots near thegreen. Furthermore, the outer covers of this invention have good impactdurability and mechanical strength.

The following test methods may be used to obtain certain properties inconnection with golf balls of the invention and layers thereof.

Hardness. The center hardness of a core is obtained according to thefollowing procedure. The core is gently pressed into a hemisphericalholder having an internal diameter approximately slightly smaller thanthe diameter of the core, such that the core is held in place in thehemispherical of the holder while concurrently leaving the geometriccentral plane of the core exposed. The core is secured in the holder byfriction, such that it will not move during the cutting and grindingsteps, but the friction is not so excessive that distortion of thenatural shape of the core would result. The core is secured such thatthe parting line of the core is roughly parallel to the top of theholder. The diameter of the core is measured 90 degrees to thisorientation prior to securing. A measurement is also made from thebottom of the holder to the top of the core to provide a reference pointfor future calculations. A rough cut is made slightly above the exposedgeometric center of the core using a band saw or other appropriatecutting tool, making sure that the core does not move in the holderduring this step. The remainder of the core, still in the holder, issecured to the base plate of a surface grinding machine. The exposed‘rough’ surface is ground to a smooth, flat surface, revealing thegeometric center of the core, which can be verified by measuring theheight from the bottom of the holder to the exposed surface of the core,making sure that exactly half of the original height of the core, asmeasured above, has been removed to within 0.004 inches. Leaving thecore in the holder, the center of the core is found with a center squareand carefully marked and the hardness is measured at the center markaccording to ASTM D-2240. Additional hardness measurements at anydistance from the center of the core can then be made by drawing a lineradially outward from the center mark, and measuring the hardness at anygiven distance along the line, typically in 2 mm increments from thecenter. The hardness at a particular distance from the center should bemeasured along at least two, preferably four, radial arms located 180°apart, or 90° apart, respectively, and then averaged. All hardnessmeasurements performed on a plane passing through the geometric centerare performed while the core is still in the holder and without havingdisturbed its orientation, such that the test surface is constantlyparallel to the bottom of the holder, and thus also parallel to theproperly aligned foot of the durometer.

The outer surface hardness of a golf ball layer is measured on theactual outer surface of the layer and is obtained from the average of anumber of measurements taken from opposing hemispheres, taking care toavoid making measurements on the parting line of the core or on surfacedefects, such as holes or protrusions. Hardness measurements are madepursuant to ASTM D-2240 “Indentation Hardness of Rubber and Plastic byMeans of a Durometer.” Because of the curved surface, care must be takento ensure that the golf ball or golf ball sub-assembly is centered underthe durometer indenter before a surface hardness reading is obtained. Acalibrated, digital durometer, capable of reading to 0.1 hardness unitsis used for the hardness measurements. The digital durometer must beattached to, and its foot made parallel to, the base of an automaticstand. The weight on the durometer and attack rate conforms to ASTMD-2240.

In certain embodiments, a point or plurality of points measured alongthe “positive” or “negative” gradients may be above or below a line fitthrough the gradient and its outermost and innermost hardness values. Inan alternative preferred embodiment, the hardest point along aparticular steep “positive” or “negative” gradient may be higher thanthe value at the innermost of the inner core (the geometric center) orouter core layer (the inner surface)—as long as the outermost point(i.e., the outer surface of the inner core) is greater than (for“positive”) or lower than (for “negative”) the innermost point (i.e.,the geometric center of the inner core or the inner surface of the outercore layer), such that the “positive” and “negative” gradients remainintact.

As discussed above, the direction of the hardness gradient of a golfball layer is defined by the difference in hardness measurements takenat the outer and inner surfaces of a particular layer. The centerhardness of an inner core and hardness of the outer surface of an innercore in a single-core ball or outer core layer are readily determinedaccording to the test procedures provided above. The outer surface ofthe inner core layer (or other optional intermediate core layers) in adual-core ball are also readily determined according to the proceduresgiven herein for measuring the outer surface hardness of a golf balllayer, if the measurement is made prior to surrounding the layer with anadditional core layer. Once an additional core layer surrounds a layerof interest, the hardness of the inner and outer surfaces of any inneror intermediate layers can be difficult to determine. Therefore, forpurposes of the present invention, when the hardness of the inner orouter surface of a core layer is needed after the inner layer has beensurrounded with another core layer, the test procedure described abovefor measuring a point located 1 mm from an interface is used.

Also, it should be understood that there is a fundamental differencebetween “material hardness” and “hardness as measured directly on a golfball.” For purposes of the present invention, material hardness ismeasured according to ASTM D2240 and generally involves measuring thehardness of a flat “slab” or “button” formed of the material. Surfacehardness as measured directly on a golf ball (or other sphericalsurface) typically results in a different hardness value. The differencein “surface hardness” and “material hardness” values is due to severalfactors including, but not limited to, ball construction (that is, coretype, number of cores and/or cover layers, and the like); ball (orsphere) diameter; and the material composition of adjacent layers. Italso should be understood that the two measurement techniques are notlinearly related and, therefore, one hardness value cannot easily becorrelated to the other. Shore hardness (for example, Shore C or Shore Dor Shore A hardness) was measured according to the test method ASTMD-2240.

Modulus, Tensile Strength and Ultimate Elongation

Modulus, tensile strength and ultimate elongation of golf ball layermaterials may be targeted as known in the art. As used herein, “modulus”or “flexural modulus” refers to flexural modulus as measured using astandard flex bar according to ASTM D790-B; tensile strength refers totensile strength as measured using ASTM D-638; and ultimate elongationrefers to ultimate elongation as measured using ASTM D-638.

Compression. As disclosed in Jeff Dalton's Compression by Any OtherName, Science and Golf IV, Proceedings of the World Scientific Congressof Golf (Eric Thain ed., Routledge, 2002) (“J. Dalton”), severaldifferent methods can be used to measure compression, including Atticompression, Riehle compression, load/deflection measurements at avariety of fixed loads and offsets, and effective modulus. For purposesof the present invention, compression refers to Soft Center DeflectionIndex (“SCDI”). The SCDI is a program change for the Dynamic CompressionMachine (“DCM”) that allows determination of the pounds required todeflect a core 10% of its diameter. The DCM is an apparatus that appliesa load to a core or ball and measures the number of inches the core orball is deflected at measured loads. A crude load/deflection curve isgenerated that is fit to the Atti compression scale that results in anumber being generated that represents an Atti compression. The DCM doesthis via a load cell attached to the bottom of a hydraulic cylinder thatis triggered pneumatically at a fixed rate (typically about 1.0 ft/s)towards a stationary core. Attached to the cylinder is an LVDT thatmeasures the distance the cylinder travels during the testing timeframe.A software-based logarithmic algorithm ensures that measurements are nottaken until at least five successive increases in load are detectedduring the initial phase of the test. The SCDI is a slight variation ofthis set up. The hardware is the same, but the software and output haschanged. With the SCDI, the interest is in the pounds of force requiredto deflect a core x amount of inches. That amount of deflection is 10%percent of the core diameter. The DCM is triggered, the cylinderdeflects the core by 10% of its diameter, and the DCM reports back thepounds of force required (as measured from the attached load cell) todeflect the core by that amount. The value displayed is a single numberin units of pounds.Coefficient of Restitution (“CoR”). The CoR is determined according to aknown procedure, wherein a golf ball or golf ball sub-assembly (forexample, a golf ball core) is fired from an air cannon at two givenvelocities and a velocity of 125 ft/s is used for the calculations.Ballistic light screens are located between the air cannon and steelplate at a fixed distance to measure ball velocity. As the ball travelstoward the steel plate, it activates each light screen and the ball'stime period at each light screen is measured. This provides an incomingtransit time period which is inversely proportional to the ball'sincoming velocity. The ball makes impact with the steel plate andrebounds so it passes again through the light screens. As the reboundingball activates each light screen, the ball's time period at each screenis measured. This provides an outgoing transit time period which isinversely proportional to the ball's outgoing velocity. The CoR is thencalculated as the ratio of the ball's outgoing transit time period tothe ball's incoming transit time period(CoR=V_(out)/V_(in)=T_(in)/T_(out)).

Thermoset and thermoplastic layers herein may be treated in such amanner as to create a positive or negative hardness gradient within andbetween golf ball layers. In golf ball layers of the present inventionwherein a thermosetting rubber is used, gradient-producing processesand/or gradient-producing rubber formulation may be employed.Gradient-producing processes and formulations are disclosed more fully,for example, in U.S. patent application Ser. No. 12/048,665, filed onMar. 14, 2008; Ser. No. 11/829,461, filed on Jul. 27, 2007; Ser. No.11/772,903, filed Jul. 3, 2007; Ser. No. 11/832,163, filed Aug. 1, 2007;Ser. No. 11/832,197, filed on Aug. 1, 2007; the entire disclosure ofeach of these references is hereby incorporated herein by reference.

A golf ball of the invention may further incorporate indicia, which asused herein, is considered to mean any symbol, letter, group of letters,design, or the like, that can be added to the dimpled surface of a golfball.

Golf balls of the present invention will typically have dimple coverageof 60% or greater, preferably 65% or greater, and more preferably 75% orgreater. It will be appreciated that any known dimple pattern may beused with any number of dimples having any shape or size. For example,the number of dimples may be 252 to 456, or 330 to 392 and may compriseany width, depth, and edge angle. The parting line configuration of saidpattern may be either a straight line or a staggered wave parting line(SWPL), for example.

In any of these embodiments a single or dual-layer core may be replacedwith a three or more layer core wherein at least one core layer has ahardness gradient.

It is understood that the golf balls of the invention incorporating aplurality of functionalized inorganic aluminosilicate ceramicmicrospheres dispersed throughout as disclosed herein and methods andtooling for making golf balls of the invention as described andillustrated herein represent only some of the many embodiments of theinvention. It is appreciated by those skilled in the art that variouschanges and additions can be made to such golf balls without departingfrom the spirit and scope of this invention. It is intended that allsuch embodiments be covered by the appended claims.

Other than in the operating examples, or unless otherwise expresslyspecified, all of the numerical ranges, amounts, values and percentagessuch as those for amounts of materials and others in the specificationmay be read as if prefaced by the word “about” even though the term“about” may not expressly appear with the value, amount or range.Accordingly, unless indicated to the contrary, the numerical parametersset forth in the specification and attached claims are approximationsthat may vary depending upon the desired properties sought to beobtained by the present invention. At the very least, and not as anattempt to limit the application of the doctrine of equivalents to thescope of the claims, each numerical parameter should at least beconstrued in light of the number of reported significant digits and byapplying ordinary rounding techniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contain certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements. Furthermore, when numerical ranges ofvarying scope are set forth herein, it is contemplated that anycombination of these values inclusive of the recited values may be used.

Although the golf ball of the invention has been described herein withreference to particular means and materials, it is to be understood thatthe invention is not limited to the particulars disclosed and extends toall equivalents within the scope of the claims.

Other than in the operating examples, or unless otherwise expresslyspecified, all of the numerical ranges, amounts, values and percentagessuch as those for amounts of materials and others in the specificationmay be read as if prefaced by the word “about” even though the term“about” may not expressly appear with the value, amount or range.Accordingly, unless indicated to the contrary, the numerical parametersset forth in the specification and attached claims are approximationsthat may vary depending upon the desired properties sought to beobtained by the present invention. At the very least, and not as anattempt to limit the application of the doctrine of equivalents to thescope of the claims, each numerical parameter should at least beconstrued in light of the number of reported significant digits and byapplying ordinary rounding techniques.

Although the golf ball of the invention has been described herein withreference to particular means and materials, it is to be understood thatthe invention is not limited to the particulars disclosed and extends toall equivalents within the scope of the claims.

It is understood that the manufacturing methods, compositions,constructions, and products described and illustrated herein representonly some embodiments of the invention. It is appreciated by thoseskilled in the art that various changes and additions can be made tocompositions, constructions, and products without departing from thespirit and scope of this invention. It is intended that all suchembodiments be covered by the appended claims.

1. A golf ball comprising a core and a cover; wherein the core includesa layer formed from a rubber composition comprising a plurality offunctionalized inorganic aluminosilicate ceramic microspheres dispersedthroughout, wherein the functionalized inorganic aluminosilicate ceramicmicrospheres have an average particle size of about 2-3 μm.
 2. The golfball of claim 1, wherein the functionalized inorganic aluminosilicateceramic microspheres are included in the rubber composition in an amountof from about 1 phr to about 10 phr.
 3. The golf ball of claim 2,wherein the rubber composition further comprises from about 25 phr toabout 45 phr of a co-agent selected from zinc salts of acrylic acidand/or methacrylic acid; zinc oxide; from about 0.3 phr to about 0.7 phrof pentachlorothiophenol and/or salts thereof; and from about 0.5 phr toabout 2.0 phr of a peroxide.
 4. A golf ball comprising an inner corelayer, an outer core layer, and a cover, wherein: the inner core layeris formed from a first rubber composition comprising a first pluralityof vinyl-functionalized inorganic aluminosilicate ceramic microspheresdispersed throughout; and the outer core layer is formed from a secondrubber composition comprising a second plurality of vinyl-functionalizedinorganic aluminosilicate ceramic microspheres dispersed throughout. 5.The golf ball of claim 4, wherein the first rubber composition and thesecond rubber composition differ in the total amount of functionalizedinorganic aluminosilicate ceramic microspheres dispersed therein.
 6. Thegolf ball of claim 5, wherein one of the first rubber composition andthe second rubber composition includes from about 5 phr to about 10 phrof functionalized inorganic aluminosilicate ceramic microspheres, andthe other of the first rubber composition and the second rubbercomposition includes from about 1 phr to about 5 phr of functionalizedinorganic aluminosilicate ceramic microspheres.
 7. The golf ball ofclaim 4, wherein the first plurality of vinyl-functionalized inorganicaluminosilicate ceramic microspheres and the second plurality ofvinyl-functionalized inorganic aluminosilicate ceramic microspheresdiffer in degree of functionalization.
 8. A golf ball comprising aninner core layer, an outer core layer, and a cover, wherein: the innercore layer is formed from a first rubber composition comprising a firstplurality of functionalized inorganic aluminosilicate ceramicmicrospheres dispersed throughout; the outer core layer is formed from asecond rubber composition comprising a second plurality offunctionalized inorganic aluminosilicate ceramic microspheres dispersedthroughout; either the first plurality of functionalized inorganicaluminosilicate ceramic microspheres or the second plurality offunctionalized inorganic aluminosilicate ceramic microspheres isvinyl-functionalized; and either the first plurality of functionalizedinorganic aluminosilicate ceramic microspheres or the second pluralityof functionalized inorganic aluminosilicate ceramic microspheres isthiol-functionalized, methacrylate-functionalized,acrylate-functionalized, epoxy-functionalized, orcarboxyl-functionalized.
 9. The golf ball of claim 8, wherein the firstplurality of functionalized inorganic aluminosilicate ceramicmicrospheres and the second plurality of functionalized inorganicaluminosilicate ceramic microspheres differ in degree offunctionalization.
 10. The golf ball of claim 8, wherein the firstrubber composition and the second rubber composition differ in the totalamount of functionalized inorganic aluminosilicate ceramic microspheresdispersed therein.
 11. The golf ball of claim 10, wherein one of thefirst rubber composition and the second rubber composition includes fromabout 5 phr to about 10 phr of functionalized inorganic aluminosilicateceramic microspheres, and the other of the first rubber composition andthe second rubber composition includes from about 1 phr to about 5 phrof functionalized inorganic aluminosilicate ceramic microspheres.